Thesis Fulltext

Pyrolysis of Waste Plastics into Fuels
A thesis
Submitted in fulfilment
Of the requirements for the Degree of
Doctor of Philosophy in
Chemical and Process Engineering

By
Feng Gao

University of Canterbury
2010
ii
iii
Summary
Waste plastic disposal and excessive use of fossil fuels have caused environment
concerns in the world. Both plastics and petroleum derived fuels are hydrocarbons that
contain the elements of carbon and hydrogen. The difference between them is that
plastic molecules have longer carbon chains than those in LPG, petrol, and diesel fuels.
Therefore, it is possible to convert waste plastic into fuels.

The main objectives of this study were to understand and optimize the processes of
plastic pyrolysis for maximizing the diesel range products, and to design a continuous
pyrolysis apparatus as a semi-scale commercial plant. Pyrolysis of polyethylene (PE),
polypropylene (PP), and polystyrene (PS) has been investigated both theoretically and
experimentally in a lab-scale pyrolysis reactor. The key factors have been investigated
and identified. The cracking temperature for PE and PP in the pyrolysis is at 450 C, but
that of PS is lower, at 320 C. High reaction temperature and heating rate can
significantly promote the production of light hydrocarbons. Long residence time also
favours the yield of the light hydrocarbon products. The effects of other factors like type
of reactor, catalyst, pressure and reflux rate have also been investigated in the literature
review.

From the literature review, the pyrolysis reaction consists of three progressive steps:
initiation, propagation, and termination. Initiation reaction cracks the large polymer
molecules into free radicals. The free radicals and the molecular species can be further
cracked into smaller radicals and molecules during the propagation reactions. -scission
is the dominant reaction in the PE propagation reactions. At last, the radicals will
combine together into stable molecules, which are termination reactions. There are three
types of cracking of the polymers: random cracking, chain strip cracking, and end chain
cracking. The major cracking on the polymer molecular backbone is random cracking.
Some cracking occurs at the ends of the molecules or the free radicals, which is end
chain cracking. Some polymers have reactive functional side group on their molecular
iv
backbones. The functional groups will break off the backbone, which is chain strip
cracking. Chain strip cracking is the dominant cracking reaction during polystyrene
pyrolysis. The reaction kinetics was investigated in this study. The activation energy
and the energy requirement for the pyrolysis are dependent on the reaction process and
the distribution of the final products. Following the equations from other literatures, the
theoretical energy requirement for pyrolyze 1kg PE is 1.047 MJ. The estimated calorific
value of the products is about 43.3 MJ/kg. Therefore, the energy profit is very high for
this process.

The PE pyrolysis products are mainly 1-alkenes, n-alkanes, and , -dialkenes ranging
from C
1
to C
45+
. The 1-alkenes and the n-alkanes were identified with a special method
developed in this research. It was found that secondary cracking process has a
significant influence on the distribution of the product. This process converts heavy
hydrocarbons into gas or light liquid product and significantly reduces 1-alkenes and ,
-dialkenes. This secondary process can be controlled by adjusting the reflux rate of the
primary product. The product of PE pyrolysis with maximized diesel range output
consist of 18.3% non-condensable gases, 81.7% w/w liquid product, and less than 1%
pure carbon under high reflux rate process. Some zeolite catalysts were tested to reduce
the heavy molecular weight wax. It was found that NKC-5 (ZSM-5) was the most
effective catalyst among zeolites tested. The proportion of the non-condensable gases
was promoted from 17% w/w to 58% w/w by adding 10% w/w NKC-5 into the PE
feedstock.

The products of PP pyrolysis are mainly methyl- oligomers. The reflux effect on the
product from pyrolysis of PP is not as great as that on PE. The PP pyrolysis product
with high reflux rate consists of 15.7% non-condensable gases, 84.2% condensed liquid
product, and less than 0.25% char. Cyclohexane is the dominant component, 21%w/w
in the liquid product. 44%v/v of the non-condensable gases is propene.

v
In the pyrolysis product of PS, there are 4% non-condensable gases, 93% liquid, and 3%
char. Styrene accounts for 68.59%w/w in the PS liquid pyrolysis products due to the
chain strip reactions. There was 19% v/v hydrogen in the gas product, which did not
exist in the PE pyrolysis gas product. The composition of the char is almost pure
carbon, which is similar to that from PE pyrolysis.

The mixture of virgin and post-consumer PE, PP and PS have also been investigated to
identify the feedstock interaction and the effect of the contamination on the product.
The interaction promotes the production of non-condensable gases. However, the effect
of the interaction on the distribution of total product is not significant. Contamination of
paper labels on the post-consumer plastics may result in higher solid residue in the
product but no significant effect on the product was found in this study.

Based on the achievements, a continuous semi-scale reactor has been designed and
constructed at maximum capacity of 27.11kg/hr in this research. From the experiments
of pyrolysis of both virgin PE and post-consumer PE on this semi-scale pyrolysis
reactor, it was found that the major components are 1-alkenes, n-alkanes, and , -
dialkenes. The distribution of the condensed products of PE pyrolysis from the semi-
scale reactor is the same as that of the products from low reflux rate process with the
lab-scale reactor. However, the proportion of non-condensable gases is much higher
than that from pyrolysis in the lab-scale tests with low reflux rate because the semi-
scale plant has higher reaction temperature and heating rate. Lower proportion of
unsaturated hydrocarbons was found in the condensed product from the post-consumer
PE pyrolysis than in the virgin PE product because of the contamination on the post-
consumer PE. The actual energy consumption for cracking and vaporizing PE into fuels
is 1.328 MJ/kg which is less than 3% of the calorific value of the pyrolysis products.
Therefore, the pyrolysis technology has very high energy profit, 42.3 MJ/kg PE, and is
environmental-friendly. The oil produced has very high quality and close to the
commercial petroleum derived liquid fuels. The experience of design and operation of
the semi-scale plant will be helpful for building a commercial scale plant in the future.
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Acknowledgement
Without the support, assistance, and motivation provided by those around me, this study
would have never been accomplished.
In particular, I would like to thank my supervisor Professor Pang for his help and
guidance during the period of research. Prof. Pang provided significant comments and
financial support on defining the topic and proceeding with the research. His assistance
in editing was very greatly appreciated. His enthusiastic nature always encourages me. I
have gained much about this study from his rigorous attitude.

I must thank CAPE department of Canterbury University and Green Fuel Technologies
Ltd. for providing the opportunity to investigate the pyrolysis technology of waste
plastic into fuels and their financial and technical assistance.

I need to thank Dr. Chris Williamson for his valuable advice. I would also like to
acknowledge the technical staffs in the department, Bob Gordon and David Brown for
teaching me the experimental techniques and how to use the analysis devices. Their
valuable suggestions, discussions, and endless enthusiasm were much appreciated.

And thanks especially to my parents, Xiangyun Gong, Xiaochen Zhu, Yanhua Lu, and
Qi Li, and all my friends who kept me encouraged throughout the five years of research
and thesis writing.
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Table of Content
SUMMARY.............................................................................................................................................. III
ACKNOWLEDGEMENT ...................................................................................................................... VI
TABLE OF CONTENT ......................................................................................................................... VII
TABLE OF FIGURE .............................................................................................................................. XI
TABLE OF TABLE ............................................................................................................................ XVII
COMMON ABBREVIATIONS USED ................................................................................................ XX
1. INTRODUCTION ............................................................................................................................ 1
1.1. BACKGROUND ............................................................................................................................ 1
1.2. ECONOMIC VALUE TO THE COMMUNITY ..................................................................................... 7
1.3. THE PYROLYSIS OF PLASTIC MATERIALS ................................................................................... 8
1.4. OBJECTIVES OF THE INVESTIGATION ........................................................................................ 11
2. LITERATURE REVIEW ON PLASTIC PYROLYSIS .............................................................. 12
2.1. FACTORS AFFECTING PLASTIC PYROLYSIS ................................................................................ 12
2.1.1. Chemical composition of feedstock..................................................................................... 12
2.1.2. Cracking temperature and heating rate .............................................................................. 14
2.1.3. Type of reactor ................................................................................................................... 18
2.1.4. Residence time .................................................................................................................... 20
2.1.5. Use of catalyst .................................................................................................................... 21
2.1.6. Pressure .............................................................................................................................. 25
2.1.7. Other Influencing factors .................................................................................................... 26
2.1.8. Multi-factor effect on pyrolysis process .............................................................................. 27
2.2. QUALITY COMPARISON OF PYROLYSIS PRODUCTS AND PETROLEUM FUELS ............................ 29
2.2.1. Review of pyrolysis monitoring and product analysis ........................................................ 29
2.2.2. Comparison of diesel with plastic derived fuels ................................................................. 30
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2.3. EXISTING COMMERCIAL PLASTIC PYROLYSIS TECHNOLOGIES AND PROCESSES ...................... 33
2.3.1. Feedstock effects ................................................................................................................. 33
2.3.2. Technology ......................................................................................................................... 34
3. ANALYSIS OF PLASTIC PYROLYSIS REACTION KINETICS AND REACTION
ENERGIES ............................................................................................................................................... 36
3.1. THEORY OF PYROLYSIS REACTIONS ......................................................................................... 36
3.1.1. Effect of thermodynamic on physical property of polymer ................................................. 36
3.1.2. Chemistry of different chain cracking type ......................................................................... 38
3.1.3. Pyrolysis reaction progresses ............................................................................................. 40
3.1.4. Reaction modelling ............................................................................................................. 45
3.2. KINETICS OF PLASTIC PYROLYSIS REACTION ........................................................................... 47
3.2.1. Reaction kinetics ................................................................................................................. 47
3.2.2. Energy balance analysis ..................................................................................................... 50
3.3. CONCLUSION ............................................................................................................................ 61
4. EXPERIMENTS: INFLUENCING FACTORS FOR PLASTICS PYROLYSIS WITH THE
HORIZONTAL FIXED-BED REACTOR ............................................................................................. 62
4.1. TEMPERATURE PROFILE OF PLASTIC PYROLYSIS ....................................................................... 62
4.1.1. Materials and methods ....................................................................................................... 62
4.1.2. Results and discussion ........................................................................................................ 65
4.1.3. Conclusions ........................................................................................................................ 69
4.2. EFFECT OF HEATING RATE ....................................................................................................... 70
4.2.1. Experimental ....................................................................................................................... 70
4.2.3. Conclusions ........................................................................................................................ 75
5. PYROLYSIS OF POLYETHYLENE AND EFFECTS OF REFLUX AND CATALYSTS .... 76
ix
5.1. PYROLYSIS OF POLYETHYLENE ................................................................................................ 76
5.1.1. Materials and apparatus .................................................................................................... 76
5.1.2. Experiment method ............................................................................................................. 81
5.1.4. Identification of the components in liquid product ............................................................. 93
5.1.5. Conclusions ........................................................................................................................ 97
5.2. EFFECTS OF REFLUX DISTILLATION .......................................................................................... 99
5.2.1. Experiments ........................................................................................................................ 99
5.2.2. Result and discussion .......................................................................................................... 99
5.2.3. Conclusions ...................................................................................................................... 113
5.3. CATALYTIC PYROLYSIS ON LOW DENSITY POLYETHYLENE ................................................... 114
5.3.1. Materials and equipment .................................................................................................. 114
5.3.2. Experimental ..................................................................................................................... 115
5.3.3. Results and discussion ...................................................................................................... 116
5.3.4. Conclusions ...................................................................................................................... 121
6. PYROLYSIS OF PP, PS AND PLASTIC MIXTURES ............................................................ 122
6.1. PYROLYSIS OF POLYPROPYLENE ............................................................................................ 122
6.1.1. Materials and apparatus .................................................................................................. 122
6.1.2. Experimental ..................................................................................................................... 123
6.1.4. Conclusions ...................................................................................................................... 132
6.2. PYROLYSIS OF POLYSTYRENE ................................................................................................ 133
6.2.1. Materials........................................................................................................................... 133
6.2.2. Experimental ..................................................................................................................... 134
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6.2.3. Result and discussion ........................................................................................................ 134
6.2.4. Conclusions ...................................................................................................................... 143
6.3. PYROLYSIS OF THE VIRGIN AND THE POST-CONSUMED PLASTIC MIXTURE .............................. 144
6.3.1. Materials and apparatus .................................................................................................. 144
6.3.2. Experimental ..................................................................................................................... 145
6.3.3. Result and discussion ........................................................................................................ 145
6.3.4. Conclusions ...................................................................................................................... 150
7. STUDY ON SEMI-SCALE PYROLYSIS PLANT .................................................................... 151
7.1. INTRODUCTION ...................................................................................................................... 151
7.2. DESIGN AND CONSTRUCTION OF THE CONTINUOUS WASTE PLASTIC PYROLYSIS SYSTEM ....... 156
7.2.1. Determination of apparatus functional sections ............................................................... 158
7.2.2. Design calculations of the pyrolysis apparatus ................................................................ 162
7.3. EXPERIMENTAL ...................................................................................................................... 168
7.3.2. Conclusions ...................................................................................................................... 180
8. CONCLUSIONS AND FUTURE WORK .................................................................................. 181
8.1. CONCLUSIONS ........................................................................................................................ 181
8.2. FUTURE WORK ....................................................................................................................... 185
REFERENCE ......................................................................................................................................... 187

xi
Table of Figure
Figure 1-1 Common expression of polystyrene molecular structure ........................ 1
Figure 1-2 A simplified expression of polystyrene molecular structure ................... 1
Figure 1-3 Marks of the seven types of plastics on various plastic products [3] ....... 2
Figure 1-4 Plastic production in the world and in Europe from 1950 to 2007 [4] ..... 3
Figure 2-1 Polymer structure, linear, branched and cross linked ............................. 13
Figure 2-2 Temperature profile along the tube reactor [12] ..................................... 15
Figure 2-3 GC analysis results of plastic pyrolysis liquid [42] ................................ 16
Figure 2-4 Influence of temperature on product distribution [44] ........................... 16
Figure 2-5 Reaction rate as a function of temperature and heating rate in pyrolysis
of Coca Cola soft drink PET bottle [51] ......................................................................... 18
Figure 2-6 Influence of residence time on the production of gaseous product (from
HDPE thermal and catalytic cracking) [65, 67] ............................................................. 21
Figure 2-7 The framework type ZSM-5 with pentasil chain parallel to z [71] ........ 23
Figure 2-8 Framework types of zeolite [52, 54] ....................................................... 24
Figure 2-9 Conversion obtained in the thermal and catalytic pyrolysis of HDPE,
LDPE, and PP (400C, 0.5h, plastic/catalyst = 50% w/w) [30] ..................................... 25
Figure 2-10 Effect of pressure on the distribution of PE pyrolysis products [77] ..... 26
Figure 2-11 Effect of pressure on the yield of gas at different temperature [77] ....... 26
Figure 3-1 The phase transitions of PET by differential thermal analysis [91] ....... 37
Figure 3-2 Effect of temperature on elastic modulus of polymers [92] ................... 37
Figure 3-3 Stability of carbon bonds [93] ................................................................ 38
xii
Figure 3-4 Proposed macroscopic mechanism of the end chain cracking of polymers
at gasliquid interface [77] ............................................................................................. 40
Figure 3-5 Sketch of random scission reaction in plastic pyrolysis [95] ................. 41
Figure 3-6 Sketch of end chain scission reaction in plastic pyrolysis [95] .............. 41
Figure 3-7 Illustration of mid chain -scission reaction [95] ................................... 42
Figure 3-8 Illustration of end chain -scission reaction (unzipping reaction) [95] .. 42
Figure 3-9 Intermolecular transfer reaction on to the end chain radicals [95] ......... 43
Figure 3-10 Intermolecular transfer reaction on the mid-chain radicals [95] ............ 43
Figure 3-11 Intra-molecular transfer isomerization via (1, 6) hydrogen transfer [95] 43
Figure 3-12 Sketch of termination reaction or radical combination reaction [95] ..... 44
Figure 3-13 Comparison of reaction energy diagrams for endothermic (a) and
exothermic reactions (b) [38] ......................................................................................... 51
Figure 3-14 Mass flow for reactant and products in PE pyrolysis ............................. 52
Figure 3-15 Formation of a 1-alkene molecule from PE molecule pyrolysis ............ 53
Figure 3-16 Products and products phases changes from PE pyrolysis ..................... 55
Figure 3-17 Relation of C
p,g
of hydrocarbons with carbon numbers [104] ................ 57
Figure 3-18 Relationship of C
p,l
of hydrocarbons with carbon numbers [104] .......... 57
Figure 3-19 Boiling point of n-alkane and 1-alkene [104] ......................................... 58
Figure 4-1 Scheme and picture of horizontal pyrolysis apparatus ........................... 64
Figure 4-2 Thermal-well 2 (left) and the combustion boat (right) ........................... 65
Figure 4-3 Temperature profile of T
1
and T
2
........................................................... 66
Figure 4-4 Comparison of space temperatures between experiment of plastic
pyrolysis and experiment without plastics ..................................................................... 67
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Figure 4-5 Non-condensable gas production at different heating rates.................... 72
Figure 4-6 Ash accumulated on both sides of a dam in the combustion boat .......... 74
Figure 5-1 Virgin LDPE feedstock .......................................................................... 76
Figure 5-2 Scheme of the vertical pyrolysis apparatus ............................................ 78
Figure 5-3 Agilent 3000A Micro Gas Chromatography .......................................... 80
Figure 5-4 Varian Gas Chromatography CP-3800 ................................................... 80
Figure 5-5 JEOL JSM 7000F high resolution scanning electron microscope .......... 81
Figure 5-6 Oil product from low (left) and high (right) reflux processes. ............... 84
Figure 5-7 High reflux rate LDPE pyrolysis process ............................................... 86
Figure 5-8 High reflux rate process pyrolysis on HDPE.......................................... 87
Figure 5-9 Micro GC analysis chart for non-condensable gases from pyrolysis of
LDPE with high reflux rate; column A (top), column B (bottom) ................................. 90
Figure 5-10 Electron microscope photo of LDPE ash surface ................................... 92
Figure 5-11 Distribution of low (top) and high (bottom) reflux rate LDPE liquid
pyrolysis products ........................................................................................................... 93
Figure 5-12 Comparison of LDPE liquid sample (top) and the liquid with additive 1-
C
16
(middle) and n-C
16
(bottom) ..................................................................................... 95
Figure 5-13 Comparison of LDPE liquid sample (top) and hydrocarbon standards
(middle and bottom) ....................................................................................................... 96
Figure 5-14 GC-MS analysis on LDPE sample diluted in n-pentane ........................ 97
Figure 5-15 Profiles of outer wall surface temperatures with empty reactor and during
LDPE pyrolysis with low and high reflux rates ........................................................... 100
xiv
Figure 5-16 Profiles of reactor space temperature (T
1
), outlet temperature from
distillation zone (T
2
) and non-condensable gas production for high reflux rate LDPE
pyrolysis process .......................................................................................................... 104
Figure 5-17 Profiles of space temperature, T
1,
from the distillation pipe during the
high flux rate pyrolysis of LDPE with comparison with baseline ................................ 105
1
2
) and gas production for medium reflux rate LDPE pyrolysis ...... 106
1
2
) and gas production for low reflux rate LDPE pyrolysis ............. 107
Figure 5-20 Distribution of the non-condensable gas components from the primary
and the secondary cracking in the LDPE pyrolysis ...................................................... 110
Figure 5-21 Comparison of pyrolysis liquid components between low reflux rate
(top) and high reflux rate (bottom) ............................................................................... 112
Figure 5-22 Catalyst appearance: (a) NKC-3A, (b) NKC-5, and (c) NKC-7 .......... 114
Figure 5-23 Gas production of LDPE catalytic pyrolysis ........................................ 118
Figure 5-24 GC analysis results for the liquid products from pyrolysis of LDPE
Chromatographs from top to bottom are respectively: Run 1 (control), Run 2 (NKC-
3A), Run 3 (NKC-5) and Run 4 (NKC-7) .................................................................... 119
Figure 6-1 Appearance of virgin PP (AR564) used in this study ........................... 122
Figure 6-2 Profiles of medium reflux rate PP pyrolysis ......................................... 125
Figure 6-3 Profiles of high reflux rate PP pyrolysis ............................................... 126
Figure 6-4 Components in non-condensable gas from PP pyrolysis ..................... 127
Figure 6-5 Comparison of liquid oil from PP pyrolysis at high (a), medium (b), and
low (c) reflux rates processes ....................................................................................... 130
Figure 6-6 GC analysis result of PP pyrolysis oil with medium reflux rate .......... 130
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Figure 6-7 Py-GC-MS chromatogram of isotactic PP at 500 C [68] .................... 131
Figure 6-8 HIPS 486B sample ............................................................................... 133
Figure 6-9 Profiles of reactor outer wall surface temperature, space temperature in
the reactor and the accumulated volume of the non-condensable gas in the PS pyrolysis
with medium reflux rate ............................................................................................... 136
Figure 6-10 Liquid product from PS pyrolysis with medium reflux rate ................. 137
Figure 6-11 Non-condensable gas production from pyrolysis of of PS, HDPE, LDPE,
and PP at medium reflux rate ....................................................................................... 138
Figure 6-12 Composition of PS pyrolysis gases with medium reflux rate ............... 139
Figure 6-13 GC chromatograph in analysis of PS liquid pyrolysis product ............ 140
Figure 6-14 Comparison of styrene standard (bottom graph) and polystyrene liquid
product (top graph) ....................................................................................................... 140
Figure 6-15 SEM image of the surfaces of PS pyrolysis ash ................................... 142
Figure 6-16 Post-consumer plastic mixture of PE, PP, and PS ................................ 144
Figure 6-17 Profiles of T
1,
T
3,
and non-condensable gas production in the pyrolysis of
post-consumer plastic mixture ...................................................................................... 146
Figure 6-18 Liquid products from individual and mixture of plastics pyrolysis...... 148
Figure 7-1 Scheme of the Niigata pyrolysis plant [89] .......................................... 152
Figure 7-2 Scheme of a fixed bed apparatus [24] .................................................. 153
Figure 7-3 Scheme of a fluidized bed apparatus [88] ............................................ 154
Figure 7-4 Scheme of a rotary kiln apparatus [45, 60] ........................................... 155
Figure 7-5 GC results of diesel (top) and PE condensable products (bottom) ....... 159
Figure 7-6 Engineering scheme of the apparatus ................................................... 160
xvi
Figure 7-7 Photo of the apparatus .......................................................................... 160
Figure 7-8 Scheme of continuous pyrolysis apparatus ........................................... 161
Figure 7-9 Photo of pyrolyzer ................................................................................ 163
Figure 7-10 Scheme and dimensions of Pot 1 .......................................................... 166
Figure 7-11 Pot 2 of the pyrolysis plant ................................................................... 166
Figure 7-12 Control panel of the apparatus .............................................................. 167
Figure 7-13 Pre-treated post-consumer PE used in the experiment. ........................ 169
Figure 7-14 GC graphs of analysis results ............................................................... 171
Figure 7-15 Temperature profiles of the continuous pyrolysis process ................... 176
Figure 7-16 Collected liquid product from pyrolysis of post-consumer PE. ........... 178

xvii
Table of Table
Table 1-1 Breakdown of the total manufactured and proportion of packaging plastic
types (2004) [7] ................................................................................................................ 4
Table 1-2 Tonnages of each type of recovered plastic in NZ in 2004 [7] .................... 4
Table 1-3 Estimated annual mass and percentage of main components in the MSW,
surveyed in Christchurch for the period from 1 July 2003 to 30 June 2004 [8] ............... 5
Table1-4 Comparison of energy density of plastics and different types of fuels [14] . 8
Table1-5 Hydrocarbon range in commercial fuels .................................................... 10
Table 2-1 Pyrolysis processes and target products [47] .............................................. 20
Table 3-1 Reaction kinetic parameters and values in pyrolysis of different plastics [79]
........................................................................................................................................ 48
Table 3-2 Literature data on kinetic parameters for plastic pyrolysis [79] ................. 49
Table 3-3 Some bond dissociation energies [38] ........................................................ 54
Table 3-4 Calculation of reaction energy change ....................................................... 54
Table 3-5 The properties of the three 1-alkenes in PE pyrolysis [104-105] ............... 56
Table 3-6 Energy balance of 1kg PE pyrolysis ........................................................... 59
Table 3-7 Calorific values of plastics pyrolysis products and net energy gain of the
process MJ/kg [10, 91] ................................................................................................... 60
Table 4-1 Product distribution at different power output ........................................... 73
Table 5-1 Physical and chemical properties of LDPE (LD N103X) .......................... 77
Table 5-2 Micro GC set points and configuration ...................................................... 82
Table 5-3 Calibration table ......................................................................................... 83
xviii
Table 5-4 Product distribution .................................................................................... 88
Table 5-5 Non-condensable gas analysis results for high reflux LDPE pyrolysis...... 89
Table 5-6 Non-condensable gas distribution and its average molecular weight ........ 91
Table 5-7 ZAF Method Standardless Quantitative Analysis ...................................... 92
Table 5-8 Energy balance of the 20g LDPE pyrolysis and vaporization .................. 101
Table 5-9 Product distribution from LDPE pyrolysis with different reflux rates ..... 108
Table 5-10 Product distribution in non-condensable gas components from primary
and secondary cracking processes ................................................................................ 109
Table 5-11 Distribution of liquid and non-condensable gas products from different
reflux rate pyrolysis processes ...................................................................................... 111
Table 5-12 Pyrolysis product distribution w/w with catalytic and comparison with
that without catalysts pyrolysis .................................................................................... 116
Table 6-1 Thermal and physical properties of virgin PP using in this study ............ 122
Table 6-2 Products from PP high reflux rate pyrolysis ............................................. 126
Table 6-3 Distribution of non-condensable gases from PP pyrolysis ....................... 128
Table 6-4 The properties of HIPS 486B ................................................................... 133
Table 6-5 Distribution of PS pyrolysis products ....................................................... 137
Table 6-6 Major components in the PS pyrolysis liquid ........................................... 141
Table 6-7 ZAF Method Standard less Quantitative Analysis ................................... 142
Table 6-8 Product distribution from pyrolysis of individual virgin plastics, and
pyrolysis of mixed virgin plastics and mixed post-consumer plastics ......................... 149
Table 7-1 New Zealand requirements for diesel regulation [130] ............................ 156
Table 7-2 Expected value of products ...................................................................... 165
xix
Table 7-3 Comparison of product distribution of different plants ............................ 173
Table 7-4 hydrocarbon distribution in the condensed product ................................. 174
Table 7-5 Theoretical energy consumption of PE pyrolysis ..................................... 179

xx
COMMON ABBREVIATIONS USED
SPI Society of Plastic Industry
PE Polyethylene
HDPE High density polyethylene
LDPE Low density polyethylene
PP Polypropylene
PS Polystyrene
PVC Polyvinyl Chloride
PET Polyethylene Terephthalate
GC Gas chromatography
MS Mass spectrometry
TGA Thermo gravimetric analysis
LPG Liquefied petroleum gases
MW Molecular weight
Micro-GC Micro gas chromatography
SEM Scanning electron microscope
EDS Energy-dispersive x-ray spectrometer
ZAF a standardless method for SEM-EDS
Norm% Normalized percentage
ZSM Zeolite Socony Mobil

1
1. Introduction
1.1. Background
Plastic is a high molecular weight material that was invented by Alexander Parkes in
1862. [1] Plastics are also called polymers. The term polymer means a molecule made
up by repetition of simple unit. For example, the structure of polystyrene can be written
in a form as shown in Figure 1-1 or in Figure 1-2.

C
H
C
H
2
C
H
C
H
2
C
H
C
H
2
C
H
2
C
H

Figure 1-1 Common expression of polystyrene molecular structure

C
H
2
C
H
n

Figure 1-2 A simplified expression of polystyrene molecular structure

The repeating unit of the polymer is in the brackets with a subscript, n, to represent the
number of the unit in this polymer molecule. [2]

Plastic is one of the most commonly used materials in daily life which can be classified
in many ways such as based on its chemical structure, synthesis process, density, and
other properties. In order to assist recycling of the waste plastic, Society of Plastic
2
Industry (SPI) defined a resin identification code system that divides plastics into the
following seven groups based on the chemical structure and applications [3]:
PET (Polyethylene Terephthalate)
HDPE (High Density Polyethylene)
PVC (Polyvinyl Chloride)
LDPE (Low Density Polyethylene)
PP (Polypropylene)
PS (Polystyrene)
Other
The above seven types of plastics are marked on various plastic products as follows [3]:

Figure 1-3 Marks of the seven types of plastics on various plastic products [3]

Due to the convenience to manufacturing and use, the world plastic production has been
increasing since it was firstly commercially manufactured, from 1.5 million tons in
1950 to 260 million tons in 2007 as shown in Figure 1-4. [4] One of the major concerns
for extensive use of the plastics is the disposal of the waste plastic. In addition, the
plastics are produced from non-sustainable oil or coal, and thus it is a non-sustainable
product. There were 30.7 million tons of waste plastic generated in the U.S. in 2007,
which accounts for 12.1% of the total municipal solid wastes. [5] In U.K., 4.9 million
tons of plastics were consumed in 2007. [6] Europe consumes about 25% of the global
plastic production, which is equivalent to 60 million tons per year. [4]
3

Figure 1-4 Plastic production in the world and in Europe from 1950 to 2007 [4]

In New Zealand, 262,904 tonnes of virgin plastics were imported for processing in 2004
and at least 71.3% (187,451 tonnes) of the plastic products were consumed domestically
with the remaining being exported. [7] The type and the quantity of the imported
plastics were given in Table 1-1. It was found that over 30% of manufactured plastics
were LDPE and 20% were HDPE.

Most cities in New Zealand have plastic collection and recycling systems, however,
only 13.5% of these post-consumed plastics (35,442 tonnes) were recovered in 2004 as
shown in Table 1-2. The majority of the recovered plastics were PE that accounted for
60% in total recovered plastics, including 35% for LDPE and 25% for HDPE. In Table
1-2, the proportions of PET and HDPE in the recycled plastics are relatively higher than
those in the imported plastic materials because these two types of plastics are identified
and separated in recycling of the municipal solid waste (MSW) in New Zealand. On the
contrary, PVC is widely used in construction that has a longer lifespan than other
packaging plastics, and there is no public recycling system for PVC. Therefore, the
proportion of the recovered PVC is relatively low.
4

Table 1-1 Breakdown of the total manufactured and proportion of packaging plastic
types (2004) [7]
Material
type Imported (ton)
Proportion in
total (%)
Used for
Packaging (ton)
PET 22,433 9 16,802
HDPE 52,587 20 21,508
PVC 39,202 15 1,372
LDPE 79,513 30 61,543
PP 32,402 12 16,233
PS 21,065 8 11,788
Other 15,702 6 8,715
Total 262,904 100 137,961

Table 1-2 Tonnages of each type of recovered plastic in NZ in 2004 [7]
Recovered plastic type
Quantity
(ton)
Proportion
(%)
PET 8,016 23
HDPE 8,932 25
PVC 2,412 7
LDPE 12,444 35
PP 1,415 4
PS 635 2
Other 1,588 4
Total 35,442 100

5
The total manufactured plastic products in New Zealand are either exported or
consumed domestically. The latter would eventually be recovered or disposed at the
landfill. In Christchurch city, 15% of the landfill wastes were plastics on average and
more detailed data are given in Table 1-3. [8] Due to high durability, plastics will not be
decomposed in decades under natural landfill conditions. As land resource is limited for
island countries, New Zealanders started to use degradable plastics or other green
materials, which are relatively high cost but certainly reduce the volume of the landfill
requirement. Christchurch City Council also started a new collection system in 2009 to
collect and separate all plastics.

Table 1-3 Estimated annual mass and percentage of main components in the MSW, surveyed
in Christchurch for the period from 1 July 2003 to 30 June 2004 [8]
Material
Quantity
(ton)
Percentage
(%)
Paper 52,225 21.5
Plastic 36,386 15
Kitchen 38,315 15.8
Green 27,975 11.5
Wood 23,875 9.8
Textiles & rubber 20,784 8.6
Rubble 16,946 7
Soil 7,306 3
Metal 8,577 3.5
Glass 5,096 2.1
Sanitary 4,019 1.7
Potentially hazardous 1,553 0.6
Total 243,054 100

6
With heavy consumption of fossil energy and fuels, the world will be faced with
shortage of energy and environmental concerns in the near future if no other solutions
are to be found. On the other hand, renewable energy sources and waste streams can be
processed for production of energy and fuels. Pyrolysis of waste plastic is an
economical method to solve waste plastic problem and to produce quality liquid fuel
which can have similar properties to the commonly used petroleum fuels.
7
1.2. Economic value to the community
The technology helps to save land resources by utilizing waste plastics to generate
valuable energy. Currently, a majority of the waste plastic is land filled and it is not
sustainable because waste plastic takes very long time to decay. [4] However, it seems
that New Zealand has no other choices but continues to do so in the foreseeable future.
New Zealand is an island country and given its limited land resources, the society as a
whole has to pay increasing attention to the environmental sustainability for the next
generations.

The worlds annual consumption of plastic which was five million tones in the 1950s
has skyrocketed to a global production of 245 million tones in 2008 and waste plastic
generation is rapidly increasing. Plastic waste is the third largest contributor to
municipal and industrial waste systems after food and paper. Christchurch produced
243054 tons of municipal refuse between July 2003 and Jun 2004 of which 15% was
plastic waste. PE, PS and PP account for over 70% of this plastic waste according to the
Christchurch City Council. [8] Therefore, significant amount of energy can be produced
with this technology. This could be an alternative energy resource for substituting fossil
fuels. The New Zealand government could reduce the reliance on the imported oils. The
community may also reduce the reliance on the hydrolic power generation.

The fuels produced from this process do not contain sulphur content because there is no
sulphur in the waste plastic feedstock. This is an advantage compared with the classic
fossil fuels such as diesel because sulphur content in the fuels could form SO
2
after
combustion. SO
2
is a pollutant causing severe air pollutions, which affects people health
and damages the concrete structure.

Therefore, this technology is environmental friendly and has significant positive impact
on the local government and community.
8
1.3. The pyrolysis of Plastic Materials
Pyrolysis is a thermal cracking reaction of the large molecular weight polymer carbon
chains under an oxygen free environment and produces small molecular weight
molecules. [9-12] Traditional treatments for post-consumed plastics were landfills or
incineration. However, landfill of the post-consumed plastics has potential problems
because of limited land resource and high durability of plastics. Incomplete incineration
may generate poisonous substances and causes serious health problems. Other methods
like gasification and bioconversion are mainly used for organic materials. [13]

HDPE, LDPE, PP and PS are all hydrocarbons consisting entirely of carbon and
hydrogen, which are similar to hydrocarbon fuels such as liquefied petroleum gas
(LPG), petrol and diesel. [14-16] Plastics are derived from petroleum and have calorific
values in a similar range as those of LPG, petrol and diesel as given in Table1-4. [14]
Table1-4 Comparison of energy density of plastics and different types of fuels [14]
Material Calorific value (MJ/kg)
Polyethylene 46.3
Polypropylene 46.4
Polystyrene 41.4
Polyvinyl chloride 18.0
Coal 24.3
Liquefied petroleum gas 46.1
Petrol 44.0
Kerosene 43.4
Diesel 43.0
Light fuel oil 41.9
Heavy fuel oil 41.1

9
Some commercial plastic pyrolysis plants have been in operation in which all types of
post-consumed plastics accepted need to be treated using hydrochloride scrubber which
is for PVC cracking and is not preferable in the fuel product because chloride is not
desirable in the fuels. [17-18] Those plants are sophisticated and not suitable for
relatively small scale production.[17] In these plants, catalysts are also used to improve
the quality of pyrolysis products in many existing equipments. Those equipments with
catalysts have some weakness in terms of long material resistance time, undesired
contact between plastics and catalysts, required high heat transfer rate, and cost of the
catalysts. [19]

In order to understand and optimise the pyrolysis of waste plastic and to investigate the
impacts of different types of the plastics, extensive research has been conducted in the
past decade. Kaminsky, Scheirs and their colleagues [17, 20-23] investigated the effects
of reaction conditions on the pyrolysis product. Williams studied the products from
pyrolysis of different individual and mixed plastics. [10-11, 24-27] Aguado et.al.
investigated the effect of catalysts on the pyrolysis reactions. [28-32] In these studies,
the lab-scale pyrolysis reactors were either batch type or semi-batch type rather than
continuous type. Most studies focused on the effects of operation temperature, heating
rate, and catalysts on the product yield. However, there are few researches in the
literature review investigating the cracking process of the pyrolysis products during the
pyrolysis which is believed to be complex. In addition, the final products are also very
complicated. There could be over a hundred of components in the hydrocarbon products
including paraffin, olefin and their isomers. Normally, the PONA system, which is an
abbreviation for paraffin, olefin, naphthene and aromatic compounds, is used to
describe those petroleum hydrocarbons. [17] Paraffins are saturated hydrocarbons with
straight or branched carbon chain, which are also called alkane. Olefins have similar
chain as paraffins, but they have one or more multiple bonds between carbon atoms in
their chains. Naphthenes are saturated hydrocarbons like paraffins but their chains
merge to a ring in their structure. Aromatics contain a benzene ring in the structure.
Another common way to describe the hydrocarbons is based on the carbon numbers in
their molecule structure. It is particularly applied to petroleum fuels. The complex
pyrolysis products may also be grouped as petroleum gases, petrol, kerosene, diesel and
10
wax. The above fuels contain hydrocarbon group with different carbon chain lengths as
given in Table1-5. [33] There are also other ways to describe the hydrocarbons such as
boiling range, phase of products at room temperature etc.

Table1-5 Hydrocarbon range in commercial fuels
Fuels LPG Petrol Kerosene Diesel* Heavy Fuel oil
Hydrocarbons C
3
to C
4
C
4
to C
12
C
12
to C
15
C
12
to C
24
C
12
to C
70

11
1.4. Objectives of the Investigation
The main objectives of this study were to understand and optimize the processes of
plastic pyrolysis for maximizing the oil products, and to design a continuous pyrolysis
apparatus as a semi-scale commercial plant. The materials to be tested in this study are
HDPE, LDPE, PP and PS which account for 70% of the plastics used in packaging.
PVC and PET are not studied due to health concerns.

This study was divided into three stages following an extensive literature review on
plastic pyrolysis. The first stage of the study focused on understanding of the thermal
cracking process and identifying key factors that affect the pyrolysis process and the
quality of the plastic pyrolysis products. From the literature review, reaction
temperature was the most important factor that influenced the whole process, however,
this study have also investigated the secondary cracking process and other significant
factors such as temperature, heating rate, type of plastic, catalysts, interaction between
different plastics, pyrolysis process, etc.. The effects of secondary cracking were
investigated. This work has not been found in other researches.

The second stage of the study was to optimize the operation conditions and the reactor
design to produce high quality liquid fuel (diesel) from the pyrolysis of LDPE.
Chemical analyses on the products were performed in this stage using gas
chromatography (GC) and mass spectrometry (MS). Char content was also analysed by
using electron microscope.
In the final stage, a continuous pyrolysis apparatus were designed and manufactured
based on the results and the information collected from the work performed during the
first two stages. The aim of this continuous apparatus was to convert LDPE and mixture
of PE, PP and PS into gas and liquid fuels with maximizing the diesel range product.
The apparatus consists of a feeding section, a pyrolysis reactor, and a separation section,
which separated diesel, wax, petrol and non-condensable gases.
12
2. Literature Review on Plastic Pyrolysis
2.1. Factors affecting Plastic pyrolysis
The major factors influencing the plastic pyrolysis process and pyrolysis product
molecular distribution include chemical composition of the feedstock, cracking
temperature and heating rate, operation pressure, reactor type, residence time and
application of catalyst. These factors are summarized in this section as follows.

2.1.1. Chemical composition of feedstock
The pyrolysis products are directly related to the chemical composition and chemical
structure of the plastics to be pyrolyzed. In addition, the chemical composition of the
feedstock also affects the pyrolysis processes. In reality, waste plastics are possibly
contaminated before recycling which could also have effects on the pyrolysis process
and products.

As mentioned in Chapter 1, PE, PP and PS are most commonly used polymeric
hydrocarbons and were selected as the investigated materials in this study. Polyethylene
is formed from ethylene through chain polymerization which is shown in Formula 2-1.
[2]
CH
2
CH
2
polymerization
n
CH
2 n
CH
2
Ethylene Polyethylene

Formula 2-1 Polymerization of ethylene to polyethylene

Plastics can be classified, according to structural shape of polymer molecules, as linear,
branched, or cross-linked in Figure 2-1. The units in linear polymer are linked only to
two others, one to each ends. The polymer is termed branched when branches extend
13
beyond the main polymer chain randomly. Regularly repeating of side groups are
considered to be part of the unit but not considered as branches. Based on the above
description, polystyrene is called linear polymer although it contains functional groups
as part of the monomer structure. In branched polymers, at least one of the monomers is
connected to more than two functional groups due to the branching points produced
from the polymerization process. The functional side group and the branch structure
have significant effects on the pyrolysis product. For example, the dominant component
in PS pyrolysis products is styrene that is the side group come off from PS carbon
backbone. [12, 34-37]

There is a significant relationship between the density and the branching intensity of
polymers. The PE with more branches has relatively lower density. This has been found
in McMurrys study. [38] The branched polyethylene is also called low density
polyethylene (LDPE), which is different from linear polyethylene that is called high
density polyethylene (HDPE). [2]

linear
branched
cross linked

Figure 2-1 Polymer structure, linear, branched and cross linked

A cross linked polymer can be described as an interconnected branched polymer with
all polymer chains are linked to form a large molecule. Thus, the cross linked polymer
constitutes large molecule. Theoretically, the molecular weight of a cross linked
polymer can be infinite. In reality, the molecular weight of a cross linked polymer will
14
be limited due to breaking down of the molecular inter-connections during the
processing or the weight of the polymer sample. The cross linked polymer cannot be
dissolved in solvents or be melted by heat because of their network structure. For
example, PEX, a common abbreviate of cross-linked polyethylene, is widely used in oil
and water piping. In pyrolysis process, cross linked polymer will crack rather than melt
or evaporate. This is different from the reactions of linear or branched polymers in
pyrolysis process.

2.1.2. Cracking temperature and heating rate
Temperature is one of the most important operating variable, since the temperature
dominates the cracking reaction of the polymer materials. Not all of the polymer
materials can be cracked by increasing the temperature. Van der Waals force is the force
between the molecules, which attracts molecules together and prevents the collapse of
molecules. When the vibration of molecules is great enough, the molecules will
evaporate from the surface of the object. [39] However, the carbon chain will be broken
if energy induced by van der Waals force along the polymer chains is greater than the
enthalpy of the C-C bond in the chain. [40] This is the reason why high molecular
weight polymer is decomposed rather than is boiled when it is heated. In theory, the
temperature of thermal breaking the C-C bonds should be constant for a given type of
plastic (polymer). However, this temperature has been found to differ in different
studies. For example, the temperature when PP starts cracking was reported at 380 C in
Ciliz et al.s result but it is measured to be 650 C in Demirbass result. [13, 41] Both of
them used similar batch process reactor and thermo gravimetric analysis. According to
the provided schemes, the most likely reason is the difference in the temperature
measurement location where the temperature sensors were located. There was
significant temperature gradient along the apparatus in which the melted plastic at the
bottom of a fix-bed batch reactor had much lower temperature than that on the top
surface of the reactor. It was also found that the space temperature in the pyrolyzer was
strongly influenced by the product vapour. Different locations of the temperature
sensors in different studies are believed to be one of the most important factors on the
different cracking temperature reported. Karaduman et al. investigated the temperature
profile along a tube heated by external furnace. [12] Large temperature variation was
15
observed between the ends and the centre of the tube. (Figure 2-2) Clearly, there was
significant heat loss at both ends of the tube reactor.

Figure 2-2 Temperature profile along the tube reactor [12]

The difference of the temperature on the surface in contact with the plastic and the
temperature of the plastic close to the surface was measured by Karaduman, A., et al.
for comparison, which is measured relatively minor and constant in this research study.
Therefore, the temperature at the reaction surface is selected for monitoring the cracking
temperature of plastics. In Shah et al.s study, mixture of post-consumed plastics of PE,
PP and PS was pyrolyzed in a fixed-bed batch reactor at different temperatures for one
hour. [42] It was found that higher reaction temperature favours the gas production and
production of heavy molecular weight products in the liquid. (Figure 2-3 and Figure
2-4) [42-43] Figure 2-3 shows the gas chromatography (GC) analysis results of the
liquid products with the temperature on the curves indicating the cracking temperature.
It is seen that the liquids produced at higher cracking temperatures have lower flash-off
percentage at the same GC temperature during the analysis. This shows higher
16
proportion of heavy molecular weight components in the liquid. Similar conclusion was
also found in other research using virgin plastics and fluidized-bed, semi-batch reactor.
[10]

Figure 2-3 GC analysis results of plastic pyrolysis liquid [42]

Figure 2-4 Influence of temperature on product distribution [44]
17
However, the overall gas proportion of gas product increased with increasing cracking
temperature up to 730C while the liquid product proportion decreased with the
cracking temperature in the full range of temperature used. (Figure 2-4)

The other operating thermal dynamic parameter is heating rate. The term heating rate
in this field means the increase of temperature per unit time. The influence of the
heating rate on the plastic pyrolysis process and product distribution varies in different
studies due to the differences in the pyrolysis reactor, operation conditions (temperature
and pressure), and temperature measurement location. Normally, in a fast or flash
pyrolysis, heating rate refers to the temperature change of the plastic from it dropped on
the hot surface till decomposed and vaporized. The hot surface remains the temperature
while the amount of plastic dropped on to it is relatively small. In this situation, the
heating rate is very high, up to 10,000 K/s. [26, 45-47] This is hard to be measured
precisely. Therefore, the surface temperature is normally applied as the reaction
temperature indicator rather than heating rate in the flash and fast pyrolysis process. In a
batch process, the plastic is normally heated from room temperature to the cracking
temperature in several minutes. It is a slow pyrolysis process. Once the plastic feedstock
is heated to the cracking temperature, the temperature remains relatively constant until
all feedstock has been pyrolyzed. Therefore, heating rate is normally applied as the
temperature indicator instead of reaction temperature in a slow pyrolysis process. It was
found that heating rate usually varied from 10 to 100 C/minute in previous slow
pyrolysis researches. [11, 24, 47-50] In Saha and Ghoshals study on pyrolysis of Coca-
Cola drink PET bottles, the influence of heating rate on the reaction process was
investigated by using thermo gravimetric analysis (TGA) as shown in Figure 2-5. [51]
In the figure, dAlpha/dT, defined as the rate of reaction (K
-1
), is plotted as a function of
absolute temperature for different heating rates from 10 to 25 K/min. It was found that
higher heating rate promotes the rate of pyrolysis reactions. [24, 52-56]

18

Figure 2-5 Reaction rate as a function of temperature and heating rate in pyrolysis of Coca
Cola soft drink PET bottle [51]

2.1.3. Type of reactor
The reactor type for the plastic pyrolysis significantly influences on the heat transfer
rate, mixing of plastics with pyrolysis products, residence time and the reflux level of
the primary products. Reactors can be classified into batch, semi-batch and continuous
or classified based on types of reactor bed.

Batch, semi-batch and continuous reactors
According to the feeding and product removal processes, the pyrolysis reactor is
categorized into batch, semi-batch and continuous reactors. In the batch reactor, the
materials are fed into the reactor in batches for pyrolysis either at the start of the process
or after all of the fed materials are processed. In the continuous reactor, the feed
materials are input from one part and the products are led out from the other part of the
reactor. A semi-batch reactor removes the pyrolysis products continuously once they are
generated but the feed materials are added initially before the pyrolysis process starts.
Some semi-batch process uses inert carrier gas to help remove the pyrolysis products.
Batch and semi-batch reactors are mainly applied on research, [24, 49-50, 57-60] and
continuous reactor is mainly for industrial production such as Mitsui R21, Fuji, Toshiba,
Veba Oel, PKA, etc. [17-18, 33, 61] Particular reactions and phenomenon such as
19
secondary pyrolysis may occur in semi-batch reactors and does not occur in batch
reactors. [28]

Fixed bed, fluidized bed and screw kiln reactors
Based on the heat transfer methods and flow patterns of the feedstock and products, the
pyrolysis reactors can be classified into fixed bed reactor, fluidized bed reactor and
screw kiln reactor. In the fixed bed reactor, the pyrolysis occurs on a stationary bed
which is easy to design and operate. However, the irregular sizes and shape of the
feedstock plastics may cause feeding problems in continuous process and the low
thermal conductivity of the plastics results in large temperature gradient in batch
process devices. In some systems, the fixed bed reactors are only used as the secondary
pyrolysis reactor because the products from the primary pyrolysis are mainly in liquid
and gaseous phase which can be easily fed into the fixed bed. [62-64]

The fluidized bed reactor has been used in most commercial plants in which gaseous
products or inert gas flow through an expanded bed of feedstock and other bed
materials, forming bubbles or eddies. The advantages of fluidized bed reactor are the
homogeneity of both temperature and composition. Heat and mass transfer rates are
much higher than the fixed bed thus the low thermal conductivity in fluidized bed
reactors is no longer a problem. In the fluidized bed reactor, the dimensions and the
material of the bed material are the key parameters affecting the pyrolysis and products.
Bed materials loss and separation from the gases are other issues which need
consideration. [61]

In recent years, a new reaction system named screw kiln reactor has been widely
applied for plastic processing. [27, 43-45] In this type of reactor, here is an extruder to
screw the feedstock from a feeder in an oxygen free environment. The extruder is
heated by external heat sources. Solid residues and pyrolysis products are separated and
collected from the other end of the extruder. The high viscosity of plastics is not a
20
problem for the flow in screw kiln reactor because the flow is driven by the external
motor. Melted plastic or even plastic solid particles can be fed into this reactor. The
small diameter of the extruder and good mixing of the materials make the radial
temperature gradient negligible. The process is relatively stable and does not use bed
material as in the fluidised bed reactor. The feeding rate can be controlled by adjusting
the rotation speed of the extruder, which also determines the residence time of plastics.

2.1.4. Residence time
The definition of residence time differs in various studies. In fast pyrolysis or
continuous pyrolysis process, it refers to the contact time of the plastic on the hot
surface throughout the reactor. However in slow pyrolysis and batch process, the
residence time means the duration from the time when feedstock plastic start to be
heated to the time when the products are removed. Longer residence time favours a
further conversion of the primary products thus yielding more thermal stable products
such as light molecular weight hydrocarbons, non-condensable petroleum gases. [31,
43, 59, 65] In a slow pyrolysis, long residence time encourages the carbonization
process and produces more tar and char in the products. [66] The pyrolysis conditions,
residence time and target products are given in Table 2-1.

Table 2-1 Pyrolysis processes and target products [47]
Process Heating rate Residence
time
Temperatur
e (C)
Target Products
Slow
carbonization
Very low Days 450-600 Charcoal
Slow pyrolysis 10-100K/min 10-60 min 450-600 Gas, oil, char
Fast pyrolysis Up to 1000K/s 0.5-5 s 550-650 Gas, oil, (char)
Flash pyrolysis Up to 10000K/s <1 s 450-900 Gas, oil, (char)
21

Except for the batch pyrolysis reactor in a closed system, residence time is difficult to
be controlled directly but can be adjusted by altering other operation parameters such as
feeding rate, carrier gas flow rate and product discharge rate. Residence time was, then,
calculated for these controllable operation parameters. [38, 46-47] Secondary pyrolysis
cracking occurs when residence time is long enough, which enhances the yield of
gaseous product. (Figure 2-6) [38, 46] Higher value of V/m represents longer residence
time in Figure 2-6. The Y axis is the conversion of HDPE to gaseous product. [65, 67]
There is a significant effect on the conversion when the residence time varies in a
certain range during the non-catalyst thermal reaction.

Figure 2-6 Influence of residence time on the production of gaseous product (from HDPE
thermal and catalytic cracking) [65, 67]

2.1.5. Use of catalyst
Advantages of using catalyst
In order to optimize plastic pyrolysis reactions and modify the distribution of pyrolysis
products, catalysts are widely used in research and industrial pyrolysis processes.
22
Petroleum fuels, such as LPG, petrol, kerosene, and diesel, are hydrocarbons from C
1
to
C
24
. The PE pyrolysis products are mainly straight hydrocarbons from C
1
up to C
80
,
which contain much more heavier molecular weight components [28] One of the main
purposes of using catalysts is to shorten the carbon chain length of the pyrolysis
products and thus to decrease the boiling point of the products. Catalysts are found to be
mainly applied to PE pyrolysis because the primary product from other plastics, such as
PP and PS, are mainly light hydrocarbons, with similar carbon chain length to the range
of commercial fuels. The products from non-catalytic PE pyrolysis contain high
proportion of 1-alkenes and dialkenes. [28, 68] Some catalysts are applied specifically
to reduce the unsaturated hydrocarbons and promote the yield of aromatics and
naphthenes. This can significantly increase the stability and cetane number of the oil
products. Moreover, it is reported that activation energies (E
a
) measured in the PE
pyrolysis with catalysts (such as HZSM-5, HY, and MCM-41) were much lower than
those when no catalyst was added. [69]

Catalyst classification
Homogeneous and heterogeneous catalysts have been studied for the catalytic cracking
of plastics. Homogeneous catalysts used for polyolefin pyrolysis have mostly been
classical Lewis acids such as AlCl
3
.[32] Generally, heterogeneous catalysts are
preferred due to their easy separation and recovery from the reacting medium.
Heterogeneous catalysts can be summarized as nanocrystalline zeolites, aluminium
pillared clays, conventional acid solids, mesostructured catalysts, superacid solids,
gallosilicates, metals supported on carbon, and basic oxides. [28] Among the mentioned
catalysts, nanocrystalline zeolites have been extensively studied for polyolefin pyrolysis
and this type of catalysts will be discussed in more details as follows.

Zeolite properties: pore size (structure) and Si/Al ratio (acidity)
A zeolite is a crystalline aluminosilicate with a three-dimensional framework structure
that forms uniform pores of molecular dimensions. [70] Zeolites act as sieves on a
molecular scale and exclude molecules that are too large to pass through the pores. The
23
three-dimensional frame structure significantly increases the area of the sieves and
absorbs molecules that have similar sizes as the pores. According to the structure of
zeolites, 176 zeolite framework types have been confirmed.[71] A three-letter code,
such as MFI, is assigned to framework types by the Structure Commission of the
International Zeolite Association.[53-54] The codes are normally derived from the name
of the zeolite, for example, MFI from ZSM-5 (Zeolite Socony Mobil-five).[72] The
MFI framework type of ZSM-5 is described as shown in Figure 2-7, with pentasil
chains running parallel to z.

Figure 2-7 The framework type ZSM-5 with pentasil chain parallel to z [71]

The pore openings and sizes are key parameters for the catalytic effect in the plastic
pyrolysis, which are determined by the size of single ring and the structure features
(cages, cavity, chains, and channels). Rings are the basic units characterize the pore
size. However, the channel wall in Figure 2-8 is composed of 6-rings and forms a 12-
ring channel. Consequently, pore opening can be influenced by the other factor,
structure feature.
24

Figure 2-8 Framework types of zeolite [52, 54]

Zeolites are crystalline micro-porous aluminosilicates. Therefore, Si/Al ratio is also an
most important parameter for zeolites which is applied to classify the zeolites.[73] The
high-silica zeolites, with a Si/Al ratio greater than five such as ZSM-5, are widely used
in petrochemical industries. [70] The high silica content in the catalyst makes the
framework to stand high temperatures that this type catalyst is suitable for high
temperature pyrolysis and regeneration cycle. A high dispersion of acidic protons
assures that each proton performs maximum acidity. [74-75] Consequently, acidity is
also an indicator to reflect the property of zeolites. Aguado et al. tested three types of
nanocrystalline zeolite with different Si/Al ratios and specific surface area. [30] High
Si/Al ratio implies a high total acidity of zeolites.[76] These zeolites are preferred for
polyolefin cracking. Lower Si/Al ratio implies lower acidity and smaller crystal size of
zeolite provide higher efficiency in terms of conversion. (Figure 2-9) The use of catalyst
is dependent on the difficulty of changing catalyst, the cost of catalyst, and the
efficiency of the catalyst. This varies in different situations.

25

Figure 2-9 Conversion obtained in the thermal and catalytic pyrolysis of HDPE, LDPE, and
PP (400C, 0.5h, plastic/catalyst = 50% w/w) [30]

2.1.6. Pressure
Operating pressure has significantly effect on both the pyrolysis process and the
products. The boiling points of the pyrolysis products are increased under higher
pressure, therefore, under pressurised environment heavy hydrocarbons are further
pyrolyzed instead of vaporized at given operation temperature. [49, 77-78] Figure 2-10
shows the effect of pressure on hydrocarbon number and their fractions in the pyrolysis
products of PE. In effect, under pressurized pyrolysis, more energy is required for
further hydrocarbon cracking. It was also found that high pressure increases the yield of
non-condensable gases and decreases the yield of liquid products. (Figure 2-11) The
average molecular weight of gas product also decreases with the increase of pressure.
[77] The influence of pressure on the concentration of double bond, C=C, of the liquid
product was not significant as reported by Murata et al. [77] In summary, pressure has
major effects on the pyrolysis reaction and the distribution of PE pyrolysis products, but
has minor effect on the double bond components.
26

Figure 2-10 Effect of pressure on the distribution of PE pyrolysis products [77]

Figure 2-11 Effect of pressure on the yield of gas at different temperature [77]

2.1.7. Other Influencing factors
There are a number of other factors which also affect pyrolysis process to a certain
extent. For example, reactive additives such as air, oxygen, or hydrogen are sometimes
27
present in the reaction for different purposes, which will interfere with the reactions and
affect the quality of the products.

Further pyrolysis of the primary product occurs in most processes. Secondary cracking
reactions were found in many reports which are enhanced by high pressure, long
residence time, low heating rate and high refluxes.[39, 41, 46, 59] Although many
researchers observed the impact of secondary cracking, few have investigated the
influence of secondary cracking process on the yield and the quality of the products.
Most secondary cracking occurred during the pyrolysis of PE and very limited cracking
was found in PS pyrolysis. This is possibly due to the difference in their primary
products. The primary products produced from PE pyrolysis contain large proportion of
heavy hydrocarbons with carbon chain number up to 80. The average molecular weight
of the primary products from PE is much higher than that of other plastics, PS, PP, PVC
and PET.[34, 60] The secondary cracking is mainly effective for heavy hydrocarbons,
hence, has less effect on the pyrolysis of PS, PVC, PET and other plastics. The
importance of secondary cracking on PE pyrolysis has intensively been studied in this
research.

2.1.8. Multi-factor effect on pyrolysis process
It is difficult to directly compare the product yields obtained for a specific plastic in
different researches as the operating conditions and reactors can be very different. In
general pyrolysis processes, thermal degradation occurs in the initial stages of the
pyrolysis with absence of oxygen. The pyrolytic products immediately after the
pyrolysis consist of solid residue, oil vapour and non-condensable gases among which
the oil vapour will become liquid after cooling down. According to the residence time
or the heating rate during the pyrolysis process, the pyrolysis can be classified into slow
carbonization, slow pyrolysis, fast pyrolysis, and flash pyrolysis. The pyrolysis process
and its target products are given in Table 2-1. [47]

28
With slow heating rate (less than 10K/min), the carbonization occurs and the process
proceeds from the outer surface to the core of the plastic particles with the local
carbonization temperature of above 300 C. The carbonization process is determined by
the heat transfer rate to the material surface and the heat transfer rate within the
material. At given temperature and heating rate, the residence time is also the most
important variable to achieve the desired carbonization. [47] The residence time
required is also related to the dimensions of the material. If the size of material is too
large which needs much longer residence time, incomplete carbonization may occur at
the centre of the plastic particles.

On the other extreme situation, if the operation temperature is very high, for example
800 to 1000 C, gasification process occurs and in this case, the plastics are directly
converted to short chain gases and the yield of non-condensable gases in the product is
maximized. High heating rate is required to minimize the proportion of solid char
production and rapid quenching favours the liquid production before further cracking
into gaseous products. [33]

The above mentioned processes are applied to all of the plastic types to be examined
including HDPE, LDPE, PP, and PS all of which have similar cracking temperature
from 320 to 500 C. However, in the pyrolysis of PVC the cracking temperature (250
C) is much lower than that of other common plastics mentioned above. [54, 78-79]

In most practical pyrolysis processes, particularly those applied in industries, preheating
and melting the plastic feedstock between 200 and 300 C are applied in order to reduce
the volume of the feedstock and to eliminate the oxygen from the feeding system. The
melting temperature is also high enough for PVC to crack and form hazardous gases
and acid. Therefore, a preheating chamber is commonly used in the commercial process
to remove gases generated from the PVC degradation in the preheating.
29
2.2. Quality Comparison of Pyrolysis Products and Petroleum
Fuels
2.2.1. Review of pyrolysis monitoring and product analysis
Pyrolysis process monitoring
In the plastic pyrolysis, plastic type and operation conditions applied in the researches
and the industries varied largely. Consequently, the variation of the yield and the quality
of the pyrolysis products are significant in the literature. However, when the same
plastic is used and same operation conditions are applied, there are similarities in the
product yield and production distribution. In most of the research work, the pyrolysis
rate of feedstock plastics is measured by using thermogravimetric analysis (TGA) in
fix-bed batch pyrolysis reactor. [9, 53] The percentage of gaseous products is measured
simultaneously with the occurrence of the reactions. In fluidized bed reactor or
continuous reactor, feeding rate is controlled and monitored to determine the reaction
rate. Operation temperature is normally monitored by using thermocouples along the
process line, which is used for estimating thermal reactions including heating-up,
decomposition, cracking, and condensation. Some studies used high pressure pyrolysis
in which pressure gauge is applied to control and monitor the operation pressure. With
these monitoring devices, the processes can be controlled by adjusting the operating
factors such as heating power, feeding rate, pressure and carrier gas flow rate when
needed. .

Product analysis method
The pyrolysis products of plastics are mainly hydrocarbons presenting in gaseous,
liquids and solid wax phases under standard conditions of temperature of 25 C and
pressure of 100 kPa. Minor amounts of char and hydrogen gas may be found in the
products. The char product can be analyzed by elemental analyzer or electron-
microscope dispersive X-ray analyzer. In research, the hydrocarbon products can be
firstly separated though gas chromatography (GC) and then identified by either
comparing with hydrocarbon standards or passing through mass spectrometry (MS).
30
The structure and the proportion of individual components are investigated in laboratory
analysis. [12, 27, 42, 56, 62, 65, 80-81]

Hydrocarbon products from industrial pyrolysis of waste plastics are used as a substitute
for commercial fuels. Instead of investigation on individual components, the
commercial fuel regulation requirements focus on the physical and chemical properties
of fuels relate to engine performance. The New Zealand regulation requirements on the
properties of petroleum fuels such as LPG, petrol and diesel adapted standard test
methods from the American Society for Testing and Materials (ASTM) and institute of
petroleum (IP) testing methods. [82] The properties of plastic pyrolysis fuels are
analyzed in some studies. [10, 22, 29, 34, 44, 52, 58, 78, 83] It was found that the
pyrolysis products from PE, PP, and PS are mainly hydrocarbons with molecular
weights similar to the petrol and diesel range. A certain amount of non-condensable
gases and insignificant amount of heavy wax were also found in the pyrolysis products.
Heavy hydrocarbon wax can be processed into gases or light liquid by further high
temperature treatments or catalytic cracking so that the yields of non-condensable gases
and wax vary largely in different studies. [52] The plastic derived fuels were also found
to have higher unsaturated hydrocarbon content and lower stability than those of
commercial fuels. [17]

2.2.2. Comparison of diesel with plastic derived fuels
The New Zealand diesel regulations have 18 requirements those can be characterized
into four groups: thermodynamic properties, flowing properties, component distribution,
and performance properties.

In the regulation for commercial diesels, one of the most important thermodynamic
properties is cetane number or cetane index that can be a substitute as cetane number,
which indicates the auto-ignition conditions of the fuel. [82, 84] Cetane index is
calculated from fuel density and distillation range which is also listed in the regulation
31
requirements. Therefore, cetane number, density, and distillation range are all important
properties to diesel fuel.

The next important properties are the fuel flow properties which include viscosity, cloud
point, pour point, cold filter plugging point and flash point. The importance of these
properties will depend on the extent of known information of fundamental properties
mentioned above, e.g., density and distillation range. If all of the fundamental properties
are well known, the flow properties are less critical.

Miscellaneous properties reflects the effects of the minorities in diesel fuels, including
carbon residues, sulphur content, water content, ash content and polycyclic aromatic
hydrocarbon content. The carbon residue is fine solid particles in the fuel that may form
combustion chamber deposits. The sulphur content in the fuel above a certain level
causes high engine wear and poisons catalysts. The water content can contribute to
corrosion in tanks and fuel injection equipment whereas the ash content is the solid
residue when fuel is burnt off. The polycyclic aromatic hydrocarbon content is used to
increase the cetane number due to their low boiling point and high density.

The properties of fuel performance consist of colour, particulate, filter blocking
tendency, lubricity, oxidation stability and copper corrosion. [84] These properties
result from one or more effects of the fundamental and the miscellaneous properties.
For example, the copper corrosion is an indicator mainly due to sulphur content in the
diesel.

Based on the diesel regulation, the fundamental properties of plastic derived fuels are
examined in most studies because the diesel fuel is produced from synthetic
hydrocarbon polymers that do not contain any other elements except for carbon and
hydrogen. Therefore, some of the miscellaneous properties are not important for the
diesel from plastic pyrolysis, such as sulphur content and water content. The quality of
32
the liquid fuels from pyrolysis of plastics will vary with pyrolysis operation conditions,
pyrolysis reactor type and types of plastic feedstock. However, comparison of the
plastic pyrolysis fuels and petroleum derived fuels has both been found in the literature
review and thus this study will investigate this in details.

The quality of plastic derived fuels varies largely based on the process and the
feedstock. The diesel range products in the LDPE derived fuels contain the same linear
chain alkanes as those in the fresh diesel. The content of alkene in LDPE derived
products is much higher than that in diesel, which decreases the storage stability of fuel.
[17] Compared to naphtha, aromatic compounds, and branched hydrocarbons, linear
alkanes have relative higher cloud point with the same carbon number or density.
Therefore, many catalysts and processes were used to reduce linear hydrocarbons and
increase the proportion of others.[17] It was found that plastic derived diesel contains
high proportion of linear alkane that has low solubility in diesel. This can significantly
increase the cloud point that is the temperature at which the first crystals appear in
diesel. Dewaxing, hydrogenation, isomerization, and cyclization are normally used in
the pyrolysis processes to change the chemical composition in the products. [25, 33, 70]
Some other properties of plastic derived fuels are controlled in the producing processes
such as distillation range and carbon residue in the fuel.

33
2.3. Existing Commercial Plastic Pyrolysis Technologies and
Processes
The waste plastic pyrolysis plants were developed and built in many countries. The
selection of the process and the plant is determined mainly on the feedstock
composition and the target products.

2.3.1. Feedstock effects
According to a summary of existing processes and technologies reported by Arena and
Mastellone, the most important property of plastic feedstock is whether it contains PVC.
[61] PVC pyrolysis has different the thermal cracking process and different products
from those of other common waste plastics including PE, PP and PS. In the PVC
pyrolysis, the products containing HCl are particularly hazardous for fuels. [54] If the
feedstock contains PVC, the plants must have re-treatment system to remove and a
solvent scrubber to remove HCl from the pyrolysis products.

The other important property for some current processes is the size of feedstock. The
requirement for the feedstock size is to avoid the feeding blockage and to enhance the
heat transfer between the heating medium and the plastics particles.

It was found that in most cases, the feedstock is a mixture of various waste plastic in
municipal slid wastes or industrial residues. In pyrolysis of the mixed plastics,
interactive effects among the different plastic types may occur due to the difference in
cracking temperatures and different products. . However, no report has been found
where the pyrolysis technology is designed for a specific type of the waste plastic. [61]

34
2.3.2. Technology
The selection of pyrolysis technology is based on the characteristics of the feedstock
and the target products. In general, each pyrolysis technology consists of three parts:
feeding system, pyrolysis reactor and separation system.

Feeding system
In most commercial processes, the raw materials are firstly heated and melted in the
feeding system before flowing into the reactor. The air, moisture and other solid
materials can be separated from the raw plastic materials in the feeding system. In
addition, the pre-treatment may be required for cracking the PVC at 250 C. [62-63] In
some rotary kiln reactors, solid plastic particles with appropriate sizes can be extruded
into the reactor directly. Most feeding systems move the highly viscous melted plastics
into reactors by its gravity or by an extruder. However, a required temperature gradient
should be maintained from the feeding system to the pyrolyzer although this may not be
an issue for the rotary kiln reactors. The required temperature gradient is to prevent
melted plastic cracking before entering the pyrolyzer. For example, the cracking
temperature of PS is 420 C thus any over heating in the feeding system should be
avoided. Free-fall feeding system is widely applied in fixed bed and fluidized bed
reactors.

Pyrolysis
The description and classification of pyrolysis reactors are given in Section 2.1 of this
thesis and the existing commercial pyrolysis plants use various types of the reactors as
summarized by Scheirs and Kaminsky. [23]

Continuous pyrolysis process is applied on most commercial plants with capability to
use catalysts in which the plastic retention time is relatively short. Very few of the
commercial plants use high pressure operation condition and most of the plants operate
35
at or slightly above atmospheric pressure. The operating temperature in the reactors
varies largely from 250 C (Mazda fixed-bed catalytic process in Japan) up to 800 C
(Compact Power fixed-bed pyrolysis in United Kingdom) but most of the pyrolysis
reactors operate between 400 C and 550 C. [23]

It must be noted that if the operation temperature is above 800 C, the process becomes
gasification and the products are mainly short chain hydrocarbons which remains as
gases under room temperature and atmospheric pressure. All of the commercial plants
are fast or flash pyrolysis. Three types of reactors including fixed-bed, fluidized-bed,
and rotary kiln can be found in the literature review. [20, 29, 45, 60-61, 65, 69, 85-88]

Product separation and collection
The products from the plastic pyrolysis are mainly combustible gases and liquids. The
liquids can be either combusted for power generation or for further refining to produce
high quality fuels. In some plants, the pyrolysis products are simply separated into
liquid, gas and solid whereas others have a more complete separation system by feeding
the mixture of liquid and gas into distillation columns. Diesel range products can then
be distilled out as in an oil refinery process. The non-condensable gases are mainly
made of hydrocarbons, and a minor amount of hydrogen and carbon monoxide. The
gases can be liquefied as fuels, or used as fuels to heat the pyrolysis reactor, or if the
amount is insignificant, the non-condensable gases are sent to an incinerator flaring off
with the air.[89] Ash may present in the non-condensable gases so most commercial
processes have a gas scrubber for cleaning the gases.

36
3. Analysis of Plastic Pyrolysis Reaction
Kinetics and Reaction Energies
3.1. Theory of Pyrolysis Reactions
Plastic pyrolysis is a complex process of breaking the long polymer chains into short
ones. In many books and researches, this thermal degradation process is usually
considered as depolymerisation of polymers.[33] In this chapter, the fundamental
phenomena involved in the pyrolysis process are investigated from both physical and
chemical point of view. Following further literature review on the reactions kinetics of
the pyrolysis reactions, heat companied with the reactions and energy demand in the
pyrolysis are analysed.

3.1.1. Effect of thermodynamic on physical property of polymer
The physical property of plastic can be changed significantly at different temperature
before the plastic decomposition temperature is reached. Over the temperature, the
carbon backbone of the plastic is cracked into shorter carbon chains. The chemical
structure of the plastics changes as well. These phenomena have been fully understood
since thermal plastics have been developed and studied for more than 100 years.[1, 90]
Under the same temperature, different types of plastics have different physical
properties and the decomposition processed may also be different.

With temperature increasing, the plastics undergo three major thermal transitions:
namely glass transition, the melting, and decomposition as shown in Figure 3-1 for the
state changes with temperature for PET. At room temperature, all polymers are hard
solids, which is also called glassy state. As the temperature rises above the glass
transition temperature, T
g
, thermoplastic acquires sufficient energy to enable the chains
to move freely and becomes rubberlike. [2] With the temperature further increasing, the
rubberlike plastic is changed to liquid-like substance when thee temperature rises above
37
the melting temperature, T
m
. Following this, the plastic starts to decompose when the
temperature reaches the decomposition temperature, T
p
. These phenomena can be
described by changes in elastic modulus of the plastics with temperature increasing as
shown in Figure 3-2. Other properties of the plastics are also changed with the
increasing temperature such as heat capacity and linage. [2]

Figure 3-1 The phase transitions of PET by differential thermal analysis [91]

Figure 3-2 Effect of temperature on elastic modulus of polymers [92]
38

3.1.2. Chemistry of different chain cracking type
The chemical changes of plastics have been investigated in order to understand the
cracking mechanism in the pyrolysis when the temperature rises above the
decomposition temperature. With the temperature increasing, the vibration of molecules
gets intensive and small molecule will escape the object surface when the vibration is
intensive enough to overcome the van der Waals force, which is called evaporation.
However, when the van der Waals force induced energy is greater than the bond
enthalpy between atoms in the molecule structure, the molecule will crack rather than
evaporate. The crackings occur at the most unstable bonds in the molecular structure.
The stability of carbon bonds in then plastics varies with the carbon bond molecular
structure and the order of stability of the hydrocarbons is shown in Figure 3-3 , in which
R is a functional group in polymers. [93]

The energy required for bond breaking is called bond dissociation energy when the van
der Waals force induced energy is equal to the bond enthalpy. The bond dissociation
energies for C-C bond of primary, secondary, and tertiary carbons are 355, 351, and
339kJ/mol, respectively. [38] Therefore, the C-C bonds on the carbons with branches
are likely to be broken first.

H
C
H
H H

H
C
H
R H

H
C
H
R R

R
C
R
R H

Methane > primary > secondary > tertiary
Figure 3-3 Stability of carbon bonds [93]

39
Based on the above theoretical analysis and other studies, three major types of cracking
in the pyrolysis reaction are proposed as described in the following sections.[33]

Random cracking
Most carbons in linear PE (HDPE) are on the long straight carbon chains (secondary
carbon atoms) so that the cracking on these carbons has the same chance to occur,
which is called random cracking. [51, 64, 94-97] There are a number of tertiary carbons
at the branched knots of LDPE. The bonds on these tertiary carbons are less stable than
secondary or primary carbons; hence, the C-C bonds at the branched knots start
cracking first. This explains the reason why most hydrocarbons from cracking of
branched LDPE carbons are straight chain hydrocarbons similar to those produced from
linear HDPE. All C-C bonds in PP joint on tertiary carbons except for few of the C-C
bonds at the ends of PP molecules. Subsequently, the bonds in PP are less stable than
those in the PE. PP is more likely to produce smaller hydrocarbons than PE. Similar
theories can be applied on the PS cracking. Random cracking is the major type of
cracking in pyrolysis of PE, PP and PS.

Chain strip cracking
Unlike the random cracking, the side carbon groups in the branched and cross-linked
polymer units may come off the main carbon chains in the pyrolysis. This process is
called chain strip cracking after which the unsaturated chains undergo further reactions
including cracking, aromatization and coke formation.[72, 77] This is the major process
in pyrolysis of polymers with reactive side groups. However, some side groups do not
significantly react. For example, chain strip cracking is not significant in PP pyrolysis.

End chain cracking
When plastic is heated to or above the decomposition temperature, the polymer may
break up from the end groups. [33, 77, 95] Figure 3-4 shows the proposed mechanism
40
of the end chain cracking to produce volatile products at the gas-liquid interface in
pyrolysis reactor. [77]

Figure 3-4 Proposed macroscopic mechanism of the end chain cracking of polymers at gas
liquid interface [77]

From Figure 3-4, it is observed that vehement molecule movements cause end chain
cracking. When the stability of the C-C bonds in chains is uniform, the chains break up
at the ends due to the vehemence of the molecule movements, which is promoted by the
temperature increase. At higher temperatures, the movements of molecules are more
vehement and thus shorter end chains will break off from the main C-C chains. This
explains the reason why high reaction temperature promotes the yield of shorter
hydrocarbon products such as in the fast pyrolysis and high temperature gasification.
[78-83]

3.1.3. Pyrolysis reaction progresses
The polymer cracking is an important reaction in the plastic pyrolysis; however, the
complete process involves other reactions as well. In this section, the full pyrolysis
reaction process will be investigated. There are numerous reactions in the plastic
41
pyrolysis process, which can be considered to consist of four stages: initiation,
propagation, hydrogen chain transfer and termination. [9, 68, 72, 77, 84-85] The
possible product species in the pyrolyzing process can be classified into two groups:
molecules including alkane, alkene, and dialkene, etc; and free radicals which also
contain unpaired electrons either at the ends or in the middle of the free radicals.

Initiation reactions
Initiation reactions break the carbon chain of polymer and form smaller free radicals
and molecules. There are three types of initial crackings according to the side group of
the plastic, which was mentioned in section 3.1.2. Initiation reactions occur randomly or
at the end chain positions in PE pyrolysis. These two types of scission reactions are
illustrated, respectively, in Figure 3-5 for the random scission reaction and in Figure 3-6
for end chain scission reaction in the plastic pyrolysis. In the figures, G represents the
side group in the polymer unit, which can be H, CH
3
or others. [95]

Figure 3-5 Sketch of random scission reaction in plastic pyrolysis [95]

Figure 3-6 Sketch of end chain scission reaction in plastic pyrolysis [95]

Massive free radicals are produced in initiation reactions; accordingly, propagation and
termination reactions are considered to be reactions of the generated free radicals.

42
Propagation reactions
Propagation is scission of the free radicals generated from the initiation reactions, which
are intermediate reactions during the pyrolysis process. From the literature review, -
scission was reported to be the main propagation reaction which also includes end chain
scission reactions and mid-chain random scission reactions. [95] These two types of
propagation reactions are shown in Figure 3-7 for the mid-chain random scission
reaction and in Figure 3-8 for end chain scission reaction. The products from the
propagation reactions are mainly 1-alkenes.

Figure 3-7 Illustration of mid chain -scission reaction [95]

Figure 3-8 Illustration of end chain -scission reaction (unzipping reaction) [95]

Propagation reactions crack the large free radicals generated from the initiation
reactions and produce alkene molecules and smaller free radicals. In macroscopic scale,
longer chain free radicals in the vapour phase are further cracked to smaller products
through the propagation reactions. This theory can be applied to explain the relationship
between residence time and the molecular weight of the pyrolysis products.

43
Hydrogen chain transfer reactions
Hydrogen chain transfer is proton transfer to other locations. This type of reactions
decreases the polymer molecular weight, which can be found in many polymerization
systems. [2] Hydrogen chain transfer reactions include intermolecular transfer reaction
(Figure 3-9 and Figure 3-10) and intra-molecular transfer reaction (Figure 3-11). [33]
Intermolecular transfer reaction occurs between free radicals and other components.
Saturated hydrocarbon molecules are formed from the corresponding radicals.

Most free radicals from the initiation are end chain free radicals, which have a positive
charge at the ends. (Figure 3-9) Some intermolecular transfer reactions on the mid-chain
radicals are shown in Figure 3-10. In the contrast, the intra-molecular transfer reactions
transfer the free hydrogen proton from the end to the middle of the free radicals. This
reaction encourages isomer production in the pyrolysis process.

Figure 3-9 Intermolecular transfer reaction on to the end chain radicals [95]

Figure 3-10 Intermolecular transfer reaction on the mid-chain radicals [95]

Figure 3-11 Intra-molecular transfer isomerization via (1, 6) hydrogen transfer [95]

44
Termination reactions
Termination reaction occurs by disproportionation of the free radicals or combining of
two free radicals as shown in Figure 3-12. [2, 33] This reaction directly affects the
product chain length.

Figure 3-12 Sketch of termination reaction or radical combination reaction [95]

As a result of the combination reaction, the final products vary largely when free
radicals from different plastics are present in the pyrolysis process.

According to the above reactions in the plastic pyrolysis, 1-alkenes are produced in -
scission reactions (propagation) while the initiation and the termination reactions
produce unsaturated compounds. Plastics like PE, PP, and PS can be considered as
saturated alkene molecules due to their large molecular weight. Therefore, the number
of unsaturated bonds in the product indicates the magnitude of initiation and termination
reactions, and the amount of 1-alkenes indicates the magnitude of propagation -
scission reactions.

The above reactions can also be described as the following reaction formula. [77, 86]
Initiation reaction:
-
R Molecule 2
(1)
Propagation (-scission) reaction:
45
-
-
+
j n j n
R O R
(2)
Termination reaction:
products R
-
2
(3)
Where
-
n
R is a free radical with a chain length n. O
j
is an alkene (olefin) with a chain
length j.

3.1.4. Reaction modelling
Due to the large number of reactions in the plastic pyrolysis processes, the reaction
models are complex and numerous. The product compounds and intermediate-products
compounds involved in the plastic pyrolysis process can be classified into molecules
such as alkane (P), alkene (O), and dialkene (D), and free radicals such as end chain
radicals and mid-chain radicals. However, free radicals exist only as intermediate
products during the pyrolysis and do not exist in the final products. [77, 86-87]
Theoretically, the reaction process models can be simplified into the following steps in
terms of the reactants and the products.

j n j n
P O P

+
(4)
) ( ) (
2 1 j n j j n j n
O O c D P c O

+ + +
(5)
j n j n
O D D

+
(6)
Where j varies along the total carbon chain length n. c
1
and c
2
are constants and their
values are dependent on the reactions and the processes. [95, 97] The straight chain
polymers can be described as large molecular weight alkenes; C
n
H
2n.
Other types of
polymers may slightly be different. If the C
n
H
2n
is assumed for all of the polymers,
based on the hydrogen balance calculation in the above steps, the ratio of alkane to
dialkene should be 1:1 if the products consist of alkanes, alkenes, and dialkenes only.
46
However, there are pure carbons and many other types of unsaturated hydrocarbons
produced in the final products. The hydrogen extracted from the pure carbons may
transfer to other products and form more saturated hydrocarbons. Large proportion of
alkenes and alkanes were found both in other literatures data and this research, which
indicates a significant effect of intra-molecular H-transfer reactions which are also
called back-biting reactions. [95, 97]

To simulate the plastic pyrolysis reactions, some reaction models have been reported in
many literatures. [62-63, 77, 86-88] Propagation reactions were extensively studied as
they have major effects on the distribution of the pyrolysis product. [97] In this work, a
more general kinetic reaction model will be developed based on the above analysis on
the plastic pyrolysis reactions and products. The model is expected to be applied to a
wider range of plastic types and pyrolysis conditions.

47
3.2. Kinetics of Plastic Pyrolysis Reaction
3.2.1. Reaction kinetics
Pyrolysis reactions of plastics are very complex. In addition, there are a number of
factors affecting the process and the reactions such as catalysts, reactor type, the type of
plastics and the secondary cracking process. A non-catalyst thermal degradation of
plastics can be generally described using the Arrhenius equation. [62, 77, 88-89]

n
km
dt
dm
=
(7)
The reaction kinetic constant in the above equation can be determined by
RT
Ea
o
e A k

=
(8)
In which m is the mass ratio of unvolatilized sample residue to the initial models of the
material before reaction and n is the reaction order. E
a
is the activation energy (kJ/mol)
and A
o
is the pre-exponential constant in the standard Arrhenius form. R is the gas
constant (J K
-1
mol
-1
) and T is the temperature in Kelvin (K).
Combining Equations (7) and (8) yields: [39, 77]
( )
n
a
o
RT
E
A
dt
d
o
o
|
.
|
\
|
= 1 exp
(9)
Where is the conversion ratio which is equal to (1-m) The kinetic parameters and the
reaction order can be determined from experiments. [39, 63, 66, 77] Marongiu et al.
applied the kinetic models for different plastics for non-catalyst pyrolysis and obtained
values for Ea, n and A
0
as given in Table 3-1. [79, 95] Products from the primary
cracking reactions can be further cracked in the subsequent reactions into lower
molecular weight hydrocarbons. [94, 98-101] The latter is also called the secondary
cracking which occurs both in non-catalyst and catalyst pyrolysis reactions.
48

Table 3-1 Reaction kinetic parameters and values in pyrolysis of different plastics [79]

From Table 3-1, it is noted that the Ea values vary from 120 to 250 kJ/mol, which may
reflect the differences in experimental conditions and test materials in application of the
kinetic reaction model. The influencing factors include molecular weight of the plastic
tested, the method of kinetic parameter estimation, the detailed forms of the kinetic
model used, the range of temperatures investigated, and other experimental conditions.
The values of activation energy and coefficient of n and A in the kinetic reaction model
(Equations 8 and 9) are summarized for different plastics types and operation conditions
are summarized in Table 3-2 in which plastics types and cracking temperature are also
given. [79, 95]

For pyrolysis reactions, Ea is the overall activation energy of all pyrolysis reactions.
The pyrolysis process and each reaction will affect the value of Ea. All of the influences
of those factors on the Ea value are not negligible, which make the evaluation of the Ea
difficult. (Table 3-2) [79, 94, 99-101] Cracking process and temperature are two
important factors affecting the value of Ea. The cracking process has very significant
effects on the composition of the final product. Large molecular weight hydrocarbons
from primary cracking can be cracked into small hydrocarbons through secondary
cracking process. The energy required in this process increases the total Ea for the
49
overall reactions. It can be observed in Table 3-1 that the Ea value increases with the
increase intensity of cracking of the products. The Ea value of LDPE cracking including
secondary crackings consumes 220kJ/mol, which is above 150% of the Ea value of
LDPE cracks into primary products only. Temperature also has effects on the Ea value
because it has significant effect on the product distribution. The results of the Ea value
at different temperature have been widely investigated and were collected by Miranda
et. al. However, it is hard to identify the influence on the Ea value from temperature
change because the experimental methods used in different literatures vary widely.
(Table 3-2) Based on the differential equations (Table 3-1), it can be deduced that the
factors influence on the Ea value by affecting the product composition. The product
with higher proportion of small hydrocarbon requires more activation energy. [79]

Table 3-2 Literature data on kinetic parameters for plastic pyrolysis [79]

*: Numbers in brackets indicate the step of pyrolysis of single plastics in literatures.
50

3.2.2. Energy balance analysis
In the plastic pyrolysis, energy may be consumed or released from different stages of
the process and reactions. This part of work aims to quantify the energy changes
throughout the pyrolysis process thus the net energy input or output can be quantified.
Three parts of energy changes are considered for the reactants and resultant substances:
reaction energy change (H), temperature change of the materials, and heat of
evaporation of the products.

The energy change during a chemical reaction is called the Gibbs free-energy change,
G. [38, 93] G consists of two terms, an enthalpy term, H, and a temperature-
dependent entropy term, TS.

S T H G A A = A
(10)
Where H is the heat of reaction (kJ/mol) and is the change in total bonding energy
during a reaction. T is the temperature in Kelvin. Generally, the enthalpy component is
dominant and much larger than the entropy component in a reaction. [38]

G has a positive value when energy is absorbed from the environment, which is called
endothermic reactions. Otherwise, it is called exothermic reaction. The relations among
potential energy, heat of reaction (H) and activation energy (Ea) are illustrated in
Figure 3-13 for both endothermic and exothermic reactions. [31]

51
(a)
(b)
Figure 3-13 Comparison of reaction energy diagrams for endothermic (a) and exothermic
reactions (b) [38]

As H is the dominant part of G, the type of reaction can be distinguished by the value
of H because of
S T H G A A = A
. In a reaction, if enough bond dissociation energies
(BDE) are known then H can be calculated. For example, the bonds in polyethylene
are almost secondary C-C bonds with bond dissociation energy of 355kJ/mol. Straight
chain hydrocarbons are the dominant products generated from PE pyrolysis. Hence, a
large number of C=C double bond and primary C-C bond at chain ends has been
produced in the reactions. 1-alkene, n-alkane, and , -dialkene are the major
52
hydrocarbons produced. 1-alkene is the major hydrocarbon product that has one C=C
double bond at one end and one primary C-C bond at the other end. There are also
minor n-alkane containing two primary C-C bonds and dialkene containing two double
bonds produced at the same time. The bond dissociation energies of the primary C-C
bond and the C=C double bond are 376 and 611kJ/mol, respectively. Both of the two
types of product bonds formed require more energy than the energy released from the
reactant secondary C-C bond breaking, 355kJ/mol. Therefore, pyrolysis of PE is an
endothermic reaction which can be confirmed by findings of previous studies..[102-
103] For a given plastic and given pyrolysis conditions, the value of H is dependent on
the composition of the final pyrolysis products.

In practical plastic pyrolysis processes, the theoretical energy required consists of heat
for increasing plastic temperature, heat for pyrolysis reactions, and heat of evaporation
of hydrocarbon products. In order to quantify the energy distribution in each part, mass
flow analysis is needed and an example for non-catalyst pyrolysis of PE is shown in
Figure 3-14 in which the pressure of the process is 101,325 Pa and the initial
temperature, T
1,
is the temperature of the feedstock at 20 C. The product temperature at
the end of pyrolysis reactions, T
2
, is 400 C at which LPG, petrol, and diesel are in gas
phase, and wax is in liquid phase which is like fog carried out by other hot gases. In this
example, LPG, petrol, diesel and wax range products are represented by hydrocarbons
C
1
~C
4
, C
5
~C
12,
C
13
~C
22,
and C
23+,
respectively. These ranges are used for the calculation
in this study only, which do not represent actual carbon number range of the fuels.

) ( % 20 ) ( % 40 ) ( % 30 ) ( % 10 ) ( liquid wax gas diesel gas petrol gas LPG solid PE
pyrolysis
+ + +

Figure 3-14 Mass flow for reactant and products in PE pyrolysis

For the plastic pyrolysis, the overall energy required for all of the matters involved can
be calculated by the following equation: [102]

53

=
in
i i
out
i i
H n H n Q
(11)

Where:
Q is the overall energy required in the plastic pyrolysis process (kJ)
n
i
is the molar number of component i (mol)
H
i
is the enthalpy of component i (kJ/mol)

For pyrolysis of PE, the products are a continuous series of straight chain hydrocarbons
which can be divided into four groups as LPG, petrol, diesel and wax represented by
C
3
H
6
, 1-C
8
H
16,
1-C
16
H
32,
and 1-C
28
H
56,
respectively. When a PE molecule is pyrolyzed
into n 1-alkene molecules, there are n-1 C-C bonds broken in the long chain. Each
secondary C-C bond is broken and turned into one C=C double bond. At the same time,
the dissociation energy of C-H bonds on the carbons with the double bond and at the
other end has also been changed. This process is described in Figure 3-15. Some bond
dissociation energies are listed in Table 3-3. [31]

-CH
2
-CH
2
-CH
2
- CH
3
-CH=CH
2
pyrolysis

Figure 3-15 Formation of a 1-alkene molecule from PE molecule pyrolysis

Using bond dissociation energies given in Table 3-3, the reaction enthalpy, H
r
, can
then be calculated using Equation (11). The calculation of bond dissociation energy
(BDE) required for forming 1-C
3
H
6
in the PE pyrolysis is shown below and the results
are given in Table 3-4. The BDE calculation for formation of 1-alkenes is similar to the
above because the mid chain does not change during the reactions and the results are
also included in Table 3-4.
54

Table 3-3 Some bond dissociation energies [38]
Bond Bond dissociation energy (kJ/mol)
C
2
H
5
- H 420
(CH
3
)
2
CH - H 401
H
2
C=CH - H 444
H
2
C=CHCH
2
- H 361
H
2
C=CHCH
2
- CH
3
310
CH3 - CH3 376
C
2
H
5
- CH
3
355
(CH
3
)
2
CH - CH
3
351
(CH
3
)
3
C - CH
3
339
H
2
C=CH - CH
3
406
H
2
C = CH
2
611

Table 3-4 Calculation of reaction energy change
Product bonds formed BDE (kJ/mol) Reactant bonds broken BDE (kJ/mol)
H
2
C = CH
2
611 4 x (CH
3
)
2
CH CH
3
4x351=1404
H
2
C=CH CH
3
406
C
2
H
5
CH
3
355
3 x H
2
C=CH H 3x444=1332 6 x (CH
3
)
2
CH H 6x401=2406
3 x H
2
C=CHCH
2
H 3x361=1083
Total 3787 Total 3810

From the results given in Table 3-4, the enthalpy change in the reactions at standard
conditions, Hr, is the difference between the total BDE in the reactants and that in the
55
products, e.g., 3787 kJ/mol 3810 kJ/mol = -23kJ/mol. This means that each mole of 1-
alkene molecular formed from PE cracking will absorb 23kJ. The energy absorbed from
the pyrolysis reactions then depends on the quantity of the molecules in the product
broken off from the polymer molecules. This result shows that pyrolysis is an
endothermic reaction.

The energy required for changing the temperature of plastic and the products can be
calculated with the following equations: [102]

}
= A A
2
1
) ( ) ( ) (
1 2
T
T
dT T Cp T H T H
(12)
Where H(T
2
) and H(T
1
) are the enthalpy of the formation of the hydrocarbons at
temperatures T
2
and T
1
, respectively
.
The phase of the hydrocarbons may change from
liquid to gas when the temperature increases from T
1
to T
2
.Cp is the heat capacity of the
hydrocarbons at a given temperature T.

When there is a phase change of the hydrocarbon between T
1
and T
2
(for example
C
16
H
32
reaction in the following calculations), the phase changes of the products are
illustrated in Figure 3-16. In this case, an evaporation energy term needs to be added
and Equations (12) is then re-written as Equation (13). In Figure 3-16 and Equation
(13), l and g represent, respectively, the liquid and gas phases of the hydrocarbons. T
b
is
the temperature at the boiling point of the hydrocarbons. The properties of the
hydrocarbons studied here are listed in Table 3-5, in which H
v
is the heat of
evaporation of the hydrocarbon. [104]
) , ( ) , ( ) , ( ) , (
2 32 16 32 16 32 16 1 32 16
1
T g H C T g H C T l H C T l H C
g
v
H
b
H
b
H

A
A A

Figure 3-16 Products and products phases changes from PE pyrolysis

56
} }
+ = A A
2
1
) , ( ) , ( ) ( ) (
1 2
T
T
T
T
b
b
dT T g Cp dT T l Cp T H T H
(13)

Table 3-5 The properties of the three 1-alkenes in PE pyrolysis [104-105]
Cp gas
J/mol K
Cp liquid
J/mol K
T
b
, 1 atm H
v
kJ/mol
C
3
H
6
64.32 112 -47.70 18.42
1-C
8
H
16
176.10 241.40 121.280 33.76
1-C
16
H
32
357.43* 470.18* 284.873 50.42
1-C
28
H
56
628.98* 810.98* 429*
Numbers with * are the calculated value from this work.

The heat capacity of gas (C
p
,
g
) and that of the liquid (C
p,l
) are in linear relationship with
the carbon numbers of n-alkane and 1-alkene as shown inFigure 3-17 and Figure 3-18
[105] It is interesting to note that with the same carbon number, the heat capacity values
of n-alkane and 1-alkene are very similar. This is true both for gas phase and liquid
phase although the values for 1-alkene are slightly lower than those of n-alkane. (Figure
3-17 and Figure 3-18) However, for heavy molecular weight hydrocarbons some
properties can not be found in the literature review, therefore, these values have been
estimated based on the existing data and linear relationship with the carbon number.
57
y =22.629x - 4.6359
R
2
=0.9999
0
100
200
300
400
500
0 5 10 15 20 25
car bon number
C
p
,
g

(
J
/
m
o
l

K
)
n-alkane 1-alkene Linear (1-alkene)

Figure 3-17 Relation of C
p,g
of hydrocarbons with carbon numbers [104]
y =28.4x +15.775
R
2
=0.9966
0
100
200
300
400
500
600
700
0 5 10 15 20 25
car bon number
C
p
,
l

(
J
/
m
o
l

K
)
n-alkane 1-alkene Linear (1-alkene)

Figure 3-18 Relationship of C
p,l
of hydrocarbons with carbon numbers [104]
The boiling points of n-alkanes from C
1
to C
100
and those of 1-alkene from C
2
to C
20

were measured at 1 atm in Wilhoit and Zwolinskis study and the results are shown in
Figure 3-19. [104] It was observed that the boiling point of 1-alkene is slightly lower
than that of n-alkane with the same carbon number in a molecule. The difference
between the boiling points of 1-alkene and the corresponding n-alkane with the carbon
number greater than 20 is less than two Celsius degrees. Therefore, the boiling point of
the corresponding n-alkane greater than C
20
can be accepted as that of 1-alkene in this
case.
58
-200
-100
0
100
200
300
400
500
600
700
800
0 20 40 60 80 100
car bon number
T
e
m
p
e
r
a
t
u
r
e

C
e
l
s
i
u
s

d
e
g
r
e
e
n-alkane 1-alkene

Figure 3-19 Boiling point of n-alkane and 1-alkene [104]

Based on Equations (13 and 14) and using data in Table 3-5, the energy required for
heating and vaporizing the product, H, can be determined and an example is shown as
Equations 15 to 18. In these equations, T
1
is the initial feedstock temperature at 25 C
and T
2
is the temperature at the end of the pyrolysis reactions, 400 C.

mol kJ dT T g Cp T H T H H
T
T
H C
b
/ 12 . 24 ) , ( ) ( ) (
2
6 3
1 2
= = A A = A
}
(14)
mol kJ H dT T g Cp dT T l Cp H T H T H H
v
T
T
T
T
v H C
b
b
/ 08 . 106 ) , ( ) , ( ) ( ) (
2
1
16 8
1 2
= A + + = A + A A = A
} }
(15)
mol kJ H dT T g Cp dT T l Cp H T H T H H
v
T
T
T
T
v H C
b
b
/ 76 . 213 ) , ( ) , ( ) ( ) (
2
1
32 16
1 2
= A + + = A + A A = A
} }
(16)
mol kJ dT T l Cp T H T H H
T
T
H C
b
/ 12 . 304 ) , ( ) ( ) (
2
56 28
1 2
= = A A = A
}
(17)

Based on the pyrolysis product described in Figure 3-14 and Equation 15 to 18, the
energy required for each individual process and the total energy required for the overall
59
process have been determined and the results are calculated in Table 3-6. The energy
required for pyrolysis of 1kg PE is 169.18 kJ. The pyrolysis process requires 697.98kJ
to heat the materials and 180.46kJ to vaporize the products. Hence, the pyrolysis
reaction is endothermic reaction. The total energy for pyrolyzing 1kg PE into products
with such distribution requires 1047.62 kJ. These figure is about 20% lower than that
proposed (1316.1 kJ/kg) by Yuan. [102] The difference is possibly due to the difference
in the reaction conditions and the distribution of products.

Table 3-6 Energy balance of 1kg PE pyrolysis
1kg PE C
3
H
6
1-C
8
H
16
1-C
16
H
32
1-C
28
H
56
Total
w/w 10% 30% 40% 20% 100%
mol 2.38 2.68 1.79 0.51 7.36
Hr kJ/mol 23.00 23.00 23.00 23.00 169.18
H kJ/mol 24.12 72.32 163.34 304.12 697.98
Hv kJ/mol - 33.76 50.42 - 180.46
Total Energy kJ 112.19 345.75 422.79 166.90 1047.62

Assuming the calorific value of these four groups of products from PE pyrolysis is close
to that of LPG, petrol, diesel, and residual oil (wax), respectively, the net energy gain by
pyrolysis of the PE plastics can be determined by
=
r i i net
Q Q w Q
(18)

Where Q
net
is the net energy gain. w
i
is the percentage of product i, which can be LPG,
petrol, diesel or wax. Q
i
is the calorific value of product i. Q
r
is the energy required in
the process which does not include the heat loss from the system. Based on the calorific
value of those commercial fuels [10, 91], the net energy gain is calculated and the
60
results are shown in Table 3-7. This net energy gain, 42.3MJ/kg, is similar to the value
reported in Yuan (41.7MJ/kg). [102]

Table 3-7 Calorific values of plastics pyrolysis products and net energy gain of the process
MJ/kg [10, 91]
Products LPG Petrol Diesel Residual
oil
Net energy profit
Composition (w./w., %) 10% 30% 40% 20%
Calorific values (MJ/kg) 46.1 44.0 43.0 41.8 42.3
61
3.3. Conclusion
Pyrolysis of hydrocarbon polymers is a very complex process, which consists of
hundreds of reactions and products. Several factors have significant effects on the
reactions and the products. Based on previous research, this chapter investigated the
fundamental plastic processes and reactions. With temperature increasing, plastic will
go though glassy state, rubbery state, liquid state, and decomposition. Decomposition of
plastic in an inert environment into liquid is called pyrolysis. There are four stages of
reactions during the plastic pyrolysis process: initiation, propagation, hydrogen transfer,
and termination reactions. In the initiation reactions, the polymer molecules undergo
three types of cracking processes: random, end chain, and chain strip cracking; which is
determined by the side functional group on the plastic molecular carbon backbone. In
the propagation reactions, especially -scission, the cracking of large molecular weight
free radicals is an important process which produces smaller compounds. Hydrogen
transfer reactions increase the variety of the free radicals and that of the final product.
Termination is the reaction that combines all free radicals into molecules.
Since the basic pyrolysis process and reactions are understood, a kinetic model was
established for energy calculation of the reactions. According to the kinetic model and
estimated product, the theoretical energy requirement for pyrolysis of PE was
calculated, 1047.62 kJ/kg. The net energy gain of the process is 42.3 MJ/kg.

62
4. Experiments: influencing factors for
plastics pyrolysis with the horizontal
fixed-bed reactor

The objective of this study is to maximize the proportion liquid range product from
pyrolysis of hydrocarbon plastics. In order to optimize the liquid range product, the
effects of factors which influence the pyrolysis process need quantifying. Many of these
factors affecting the distribution of the products were identified in previous studies and
this has been discussed in Section 2.1. However, some of the factors can not be
controlled in the process under the reaction conditions. Those adjustable factors will be
controlled to optimize the process and to achieve the study objective. In this part of the
study, a series of experiments were designed to identify and quantify the effect of the
factors on the process and the distribution of the products. According to the results and
the findings from each experiment, the apparatus and reaction conditions were modified
to maximize the proportion of liquid product.

4.1. Temperature profile of plastic pyrolysis
4.1.1. Materials and methods
In this work, a horizontal fixed-bed batch reactor was designed and constructed as
shown in Figure 4-1. The goal for this experiment was to understand the process of the
plastic pyrolysis by monitoring and analyzing the temperature profile. In the system, a
M303PY Gallenkamp electronic furnace was applied to heat the reactor as an external
heating resource. There are two heating sources in the furnace. The front one was used
for heating the reactor in this experiment, which has a maximum power output of 881
W. The output power was dialled at Load 100 to provide its maximum power. The
reactor was made of stainless steel pipe with an inner diameter of 28 mm and thickness
of 2 mm. The system also consists of nitrogen purging bottle and a water-cooling
63
condenser, both of which are connected to the reactor. Connected to the condenser are a
liquid collector and a gas collector. The temperature on the outer wall of the reactor was
measured by using thermocouples 1 (Thermal-well 1) and the centre space temperature
in the reactor was measured using thermocouple 2 (Thermal-well 2). Thermal-well 2 is
shown in Figure 4-2(left).

The experiments used materials supplied by a plastic recycling company which was a
mixer of 50% PE, 25% PP, and 25% PS (weight) in the form of post-consumer plastic
chips. During the experiment, 10.00 grams of the supplied materials sample chips were
placed in the centre section of a combustion boat inside the reactor that was for
maintaining consistency of the sample location in the reactor. The combustion boat was
half of a pipe that was separated into three sections. (Figure 4-2 right) The centre
section was at the heating zone of the furnace, which had the highest temperature in the
process.

After the test plastic chips were placed in the reactor, the system was sealed and the
nitrogen gas was used as an inert gas to purge the whole system before the furnace
started heating. This lasted about one minute. ) When the pyrolysis started and the
plastics was heated and then decomposed once the temperature is high enough, the
gases produced went through the water-cooling condenser and the temperature was
reduced to about 30 C. Liquid and non-condensable gases were separately then
collected separately. The process ended when no more products came out and the space
temperature raised above 500C.

Non-condensable gas product was collected by a water sealed gas cylinder with which
the volume of collected gases can be read during the reaction process. It was found that
brown wax accumulated at the two ends in the combustion boat. The liquid products are
yellow-brown oils.

64

Figure 4-1 Scheme and picture of horizontal pyrolysis apparatus
65

Figure 4-2 Thermal-well 2 (left) and the combustion boat (right)

In order to analyse the temperature changes during the plastics pyrolysis, a separate
experiment was performed without any feedstock under the same conditions as the
previous one. In the experiments, the temperature and the non-condensable gas volume
was recoded every one minute.

4.1.2. Results and discussion
The 10g plastic mixture was completely pyrolyzed and after the experiment almost
nothing was left in the central section of the combustion boat. The products collected
included non-condensable gases in the gas collector, dark brown liquid in the liquid
collector, yellow or brown wax and char in the reactor. Then the non-condensable gas
was pumped into a balloon with an aluminium inner layer.

The wall temperature, T
1
, and the space temperature, T
2
, were simultaneously measured
during the experiments and the results are shown in Figure 4-3 for the experiment with
plastics in the reactor. From Figure 4-3, it was found that large temperature gradient
existed between the reactor outer wall and the space inside the reactor. Towards the end
of the experiment, both temperatures (T
1
and T
2
) approached constant values of 1030 C
66
and 500C, respectively. This was also found in the temperature profile from other
researches. [9, 34-35] There was an increase on the T
2
curve from the 16
th
minute to the
20
th
minute. However, this is not observed on the T
1
curve. This means the temperature
of the gas in the reactor had a sudden change during this period. Due to the small
quantity of the mass of gas, the effect of this temperature change on the wall of the
reactor was too minor to be detected by T
1
. (Figure 4-3)

0
200
400
600
800
1000
1200
0 100 200 300 400
Heati ng Ti me [mi n]
T
e
m
p
e
r
a
t
u
r
e

(
o
C
)
T1
T2

Figure 4-3 Temperature profile of T
1
and T
2

In order to examine and explain the sudden increase on the T
2
curve at the pyrolysis
period of 16 to 20 minutes from the start, the temperature profiles from the separate
experiment without plastics can be used as the baseline. In the latter experiment
(without plastics), other conditions remained the same as those in the previous
experiment so that the baseline curve can be plotted to compare with the temperature
curve with 10g plastic mixture in the reactor. (Figure 4-4) The two temperature profiles
are the same from the beginning to the 16
th
minute. The temperature curve with 10g
plastic rapidly increased from the 16
th
and reached the peak at the 18
th
minute. The
temperature then dropped to the baseline curve at the 20
th
minute. The 10g plastic
67
reaction temperature curve is slightly lower than the baseline curve after the 20
th

minute.

0.0
100.0
200.0
300.0
400.0
500.0
0 20 40 60 80 100
Heating time (min)
T
e
m
p
e
r
a
t
u
r
e

(
o
C
)
nitrogen only with 10g plastic mixture

Figure 4-4 Comparison of space temperatures between experiment of plastic pyrolysis and
experiment without plastics

At the 16minute of plastic pyrolysis experiment, the temperature of the reactor wall
reached 480C. Considering the high heat conduction rate of the 2 mm thick stainless
steel pipe, the temperature of the plastics in the reactor was very likely to be below but
close to the reactor wall temperature of 480 C. The specific cracking temperature of the
plastic tested cannot be identified because the feedstock plastic was a mixture of 50%
PE, 25% PP, and 25% PS. In addition, the post-consumer plastics were possibly
contaminated during the consumption process. In the further studies, virgin plastics
were tested individually in order to determine the cracking temperature of each type of
plastics and this will be described in Chapter 5.

From Figure 4-4, it is also observed that the space temperatures in the two experiments
were almost the same from the starting to the 16
th
minute which means the energy
required for increasing the plastic temperature was not significant enough to make
68
difference on the space temperature. That is due to the small quantity of mass and
relatively low heat capacity of the plastics. At the 16
th
minute, plastics were cracked and
vaporized into the reactor space. The temperature of the hydrocarbon vapour was close
to 480 C which is higher than the baseline space temperature of 110 C. According to
other literatures and previous discussion in section 3.1.3, plastics start with random
cracking during which a series of hydrocarbon products such as non-condensable gases
(C
1
to C
4
) will be produced. [13, 33, 52, 106-107] As the volume of the pipe reactor is
250 ml, the volume expansion could be detected instantly with negligible time delay.
Therefore, the gases could flow out of the reactor instantly once being generated.. This
can be confirmed by the volume increase of the non-condensable gases and in this way
the on-condensable gas volume measurement can be regarded as the most sensitive
parameter for indicating the random cracking at the beginning of the plastic pyrolysis.
The condensable vapour formed liquid products during the cooling process in the
condenser.

By further examining the temperature profiles in the plastic pyrolysis (Figure 4-3) and
comparison with the baseline temperature (Figure 4-4), it is believed that the sudden
increase in the space temperature towards the outer wall temperature occurred when the
gases were generated. Hence, during the plastic pyrolysis experiments, a rapid
temperature rise in space temperature, T
2
, caused by the hot vapour can be used as
another sensitive indicator of vaporization and cracking of plastics. In the plastic
pyrolysis experiment, the fast vaporization period lasted bout 2 minutes from 16 to 18
th

minutes from the start. It is interesting to see that the space temperature rise followed a
single curve indicating the three types of plastics were vaporized during this period;
therefore, they had similar cracking temperatures.

After the short period of fast cracking, it took another two minutes for the space
temperature to drop back to the baseline, which means the energy required for the
plastic cracking and vaporizing were not detectable and insignificant compared to the
heat used for heating up of the system.

69
In the experiment, because a horizontal reactor was used, some of the heavy molecular
hydrocarbons could be condensed bear the cooler ends of the reactor which were
exposed to the ambient air. With increase in the reactor outer wall temperature, the
condensed hydrocarbons may be re-vaporized and re-condensed at the ends of the
reactor. This reflux process absorbed and caused loss of a significant amount of heat. In
addition to the above heat consumed and lost, the outflow gases would carry away some
heat from the reactor. As a result, the space temperature curve in the plastic pyrolysis
was lower than the baseline curve in the experiment without plastics after 20 minute
from the start (Figure 4-4), and the difference between them became greater while the
process proceeded. The energy consumption of the process was estimated in chapter 5.

4.1.3. Conclusions
Post-consumed polyethylene, polypropylene, and polystyrene were tested in order to
understand the first cracking process on these common waste plastic. It was found that
these plastics have similar cracking temperature and the cracking process which lasted
about two minutes. All of the three types of waste plastic were cracked when the reactor
outer wall temperature was below 480C. It was found that condensation and
vaporization of the pyrolysis vapour near the ends of the reactor required and caused
loss of a significant amount of heat. However, the energy required for cracking the
plastics was insignificant to be to be detected. Large temperature gradient between
reactor wall and inside space was detected in the experiment. The temperature on the
reactor wall is believed to be close to the cracking temperature of the plastic.

Based on the above findings, the production of non-condensable gases can be used as a
sensitive indicator for random cracking reactions (primary cracking), thus the
measurement of gas volume can determine the time when plastic starts cracking. The
space temperature is another sensitive indicator for detecting when the product vapour
generated by the cracking process.

70
4.2. Effect of Heating Rate
Heating rate can be defined in many terms on various pyrolysis plants and researches.
In a fast or flash pyrolysis, plastic will be cracked and vaporized very quickly once
entering the pyrolysis reactor. In these cases, the heating rate hereby means the rate of
temperature increasing per unit time during the contacting time, which can range from
100 up to 10000 K/s. [10] On contrast, in a slow pyrolysis or a batch process, heating
rate is normally from 10 to 100 K/s or less. [10] However, in practice, the most
convenient way to control the heating rate is to control the heating load to the pyrolysis
reactor at given feeding rate. The effect of the heating rate has been discussed in Section
2.1.2. It has been found that heating rate has both effect on the pyrolysis reaction rate
[51] and the effect on the distribution of products. [10, 31, 42, 44, 106, 108]

The aims of this part of experimental studies were to experimentally examine the effect
of heating rate on the pyrolysis process and the product distribution, and to identify how
temperature triggered the cracking of the plastic mixture under the experimental
conditions.

4.2.1. Experimental
The apparatus described in previous section was used in this part of the study as
illustrated in Figure 4-1. The key part of the system is the M303PY Gallenkamp
electronic furnace which provides heat with adjustable output power load controlled at
scale from 0 to 100. The same post-consumed plastic mixture as that in the previous
experiment was used in this experiment. The experiment consisted of three runs with
different power load settings at 60, 80 and 100 with the full scale (100) being equivalent
to the maximum power output of 881 W. 10g post-consumed plastic mixture was used
in each run. Pyrolysis products of non-condensable gas, liquid and solid were collected
separately. The volume of gas product, reactor outer wall temperature (T
1
),

reactor
space temperature (T
2
) were measured and recorded every minute simultaneously
during each run of the experiment.
71

The measured accumulated volume of non-condensable gas product was shown in
Figure 4-5 for each run of the experiment. From the figure, it is found that the non-
condensable gas started to be generated when the wall temperature reached a certain
temperature, 450 C, in all three runs. This start of gas generation indicated the
corresponding start of plastic cracking. To examine the pyrolysis process, the
temperature variation within the reactor needs to be considered. As the heat is
transferred from the heating element to the plastics through firstly the reactor wall and
then the combustion boat, a temperature gradient must exist in the reactor radius
direction. Therefore, a temperature gradient exists between the reactor wall and the
surface of the combustion boat. In addition, there is also a temperature gradient alone
the horizontal direction (length) of the combustion boat due to heat loss from the two
ends of the reactor. Consequently, the central part of the reactor is hotter than the two
ends and this was also observed in other study. [12]

In the experiment, the test sample of plastic mixture was placed horizontally in the
combustion boat. The plastic at the central zone of the boat would start cracking earlier
than those at the ends because of the temperature gradient along the reactor length.
Although it was unable to determine exactly the hottest spot in the combustion boat, the
outer wall temperature at the middle of the reactor was used as an indicating factor that
determined the start point of the plastic cracking. It should be noted that the actual
cracking temperature can be slightly different and likely to be lower than the outer wall
temperature due to the temperature gradients both in the reactor radius and along the
length of the combustion boat. This has also been discussed in other studies. [12, 31, 54-
55, 79, 87, 109]

72
0
1
2
3
4
5
6
0.0 20.0 40.0 60.0 80.0 100.0 120.0
Reacti on ti me (mi n)
V
o
l
u
m
e

o
f

n
o
n
-
c
o
n
d
e
n
s
a
b
l
e

g
a
s

(
L
)
Load 60 Load 80 Load 100

Figure 4-5 Non-condensable gas production at different heating rates

During the plastic pyrolysis, the changes in space temperature in the reactor were
caused by the vapour generated from the plastic cracking reactions and the space
temperate was lower than the plastic temperature in the combustion boat. Therefore, it is
not suitable to use the space temperature as the plastic cracking temperature but this
indicates the temperature of vapour leaving the reactor.

As the heating rates in the pyrolysis experiments increased with increasing of the power
output from setting scale of 60 to the scale of 100, the corresponding heat-up times were
30, 22 and 13 for the reactor to be heated to the temperature when the plastic cracking
occurred. The LDPE cracking point can be identified by the start of gas generation as
well as the space temperature rapid increase. (Figure 4-5 and Figure 4-4) The LDPE
cracking point remained at 450 C, which does not affected by the heating rate As
Figure 4-5 shows the accumulated volume of the non-condensable gases, the slope of
the curves are the generation rate of the non-condensable gases per unit time. The
results of the slope calculations show that the gas generation rate was the lowest for the
60 scale power output and the highest for the 100 scale power output. In other words,
73
the gas production rate also indicates the intensity of the random cracking during the
plastic pyrolysis. Therefore, the heating rate has a positive relationship with the
intensity of random cracking reactions.

From the temperature profiles shown in Figure 4-3, it is found that the space
temperature inside the reactor reached a constant value towards the end of the pyrolysis
process. In a similar way, the reactor wall temperature also approached a constant value
towards the end of the pyrolysis process and the value of the constant wall temperature
was also positively related to the power output. At the same ambient conditions, the
constant wall temperature was 617, 680, and 800 C with power load setting at 60, 80,
and 100, respectively.

Table 4-1 Product distribution at different power output
Product (g) Power output scale
100 80 60
Oil 2.08 3.5 4
Gas* 5.86 3.49 1.87
Gas volume (L) 5.10 3.30 1.67
Char 1.22 1.28 1.3
Wax 0.84 1.73 2.83
Total 10 10 10
Note that: * the mass of gas product is a calculated from mass balances based on other
collected products and the total mass of the feedstock.

The non-condensable gas and liquid products collected are given in Table 4-1. In
addition to the gas and liquid, wax product was also found in the combustion boat (at
the two end zones) after the plastic pyrolysis was completed. The quantity of the wax
74
collected was more for lower heating rate test and less for the high heating rate test. The
explanation for this is that at high temperatures, wax initially condensed at the ends was
further cracked and vaporized into gas and liquid products. Therefore, the run with
maximum power output has the highest proportion of gas product and the lowest
proportion of wax. (Table 4-1) The gas production and the wax production have a
reverse proportional relationship.

In the plastic pyrolysis, char product was also found accumulating near the two dams in
the combustion boat which was mainly from the labelling in the waste plastic. (Figure
4-6) According to other study, slow pyrolysis promotes char production. [47] The heat
from the bottom of the combustion boat was conducted to the dams, which created slow
pyrolysis zones. This can be confirmed by the observation that the char was found on
both sides of the dam but was not found at the centre of the combustion boat. It is
interesting to note that some small quantity of char was found in the end zones of the
combustion boat near the dams which indicates that secondary cracking of the
condensed wax would also produce some char in addition to gas and light liquid. The
char could have effect on the heat transfer of the combustion boat.

Figure 4-6 Char accumulated on both sides of a dam in the combustion boat
In order to avoid wax accumulation and char production inside the pyrolysis reactor, the
reactor was later modified and reinstalled vertically, and this will be discussed in the
following chapter of this thesis.
75

At the beginning of the pyrolysis reactions, the curves of non-condensable gas volume
in the three runs increased with various slopes. This phenomenon may be due to the
heterogeneity nature of the plastic mixture because PE, PP, and PS has different thermal
properties and produces different pyrolysis products. In order to identify the process and
the products precisely for each type of the plastics, further investigation was performed
for pyrolysis of individual type of plastics and this will be described in next chapter.

4.2.3. Conclusions
Non-condensable gas, oil, wax, and char were the final products in the pyrolysis of
waste plastic. From this part of study, it was concluded that the rapid production of non-
condensable gases were generated from random cracking at the beginning of the
pyrolysis. Heating rate has a positive relationship with the intensity of random cracking
reactions thus more non-condensable gas, less liquid oil and less wax were produced
with higher heating rate pyrolysis. The heating rate does not significant affect the char
production although the char content tended to be less with high heating rate.

The temperatures measured at the reactor wall and in the inside space were both
affected by the heating rate in the plastic pyrolysis. Both temperatures were higher for
higher heating rate, which promotes further cracking of the wax and produces lighter
hydrocarbons. Due to the variations in the reactor, the plastic cracking first occurred at
the hottest spots which temperature would be close to but lower than the reactor wall
temperature. Space temperature can be used as an indicator as the temperature of
outflow vapour from the reactor.
The current batch pyrolysis system has shown the wax condensation near the ends of
the reactor thus it was modified and installed vertically. This new reactor will be used to
investigate the pyrolysis process of individual types of plastics and to examine the
effects of other operation parameters. This will be discussed in the following chapter.
76
5. Pyrolysis of Polyethylene and effects of
reflux and catalysts
5.1. Pyrolysis of Polyethylene
5.1.1. Materials and apparatus
As different types of plastics behave differently in pyrolysis process, the major three
types of plastic, polyethylene (PE), polypropylene (PP) and polystyrene (PS) were
investigated on the batch pyrolysis apparatus. The plastics used in this series of
experiments were virgin plastic particles for the fundamental investigations thus the
material variability can be eliminated. All of these particles were granular particles with
dimensions of approximately 3 mm long and 3 mm wide. (Figure 5-1) This chapter will
discuss the pyrolysis of low density polyethylene (LDPE) with high density
polyethylene (HDPE) is also pyrolyzed for comparison studies. In this chapter, effects
of catalyst and reflux distillation are also presented.

Figure 5-1 Virgin LDPE feedstock

77
The low density polyethylene particles were produced by the state-of-the-art DSM
Stamicarbon tubular process for blown film process. The chemical and physical
properties of the LDPE were provided by PETLIN (Malaysia) Sdn Bhd. (Table 5-1)

Table 5-1 Physical and chemical properties of LDPE (LD N103X)
Properties Units Typical values Test methods
Relative density kg/m
3
921 ISO 1183 (A)
Bulk density kg/m
3
590 -
Melting point C 110 DIN 53765
Softening point C 91 ISO 306
Modulus of elasticity TD N/mm
2
260 ISO R527-3

In the experiments of this chapter and next chapter, the pyrolysis apparatus was
modified to a vertical pyrolysis reactor in order to control the wax and to generate a
distillation zone above the pyrolysis reactor. The modified apparatus is shown in Figure
5-2, which consists of three major components: a furnace, a reactor with a distillation
pipe and a condenser. The pyrolysis reactor and the distillation pipe are connected
together and became two functional zones: the bottom zone for the pyrolysis and the top
zone above the furnace for the distillation. The reflux rate in the distillation zone can be
adjusted by changing the length of the pipe which is naturally cooled by the ambient air
around the top part. Three different pipes were used which had lengths of 380 mm, 280
mm and 200 mm, respectively, corresponding to high, medium and low reflux rates in
the pyrolysis tests. With high reflux rate in the process, the residence time of the heavy
products will be longer than that with low reflux rate process.

Three thermowells were mounted on the apparatus for installing thermal couples.
(Figure 5-2) Thermal couple 1 (T
1
) is for measuring the space temperature over the
78
pyrolysis reactor and below the distillation zone. The thermocouple locates 200mm
below the top of the reactor pipe. Thermocouple 2 (T
2
) is located at the entrance of the
condenser that also is the outlet of the distillation zone, which measured the temperature
of the product flowing out of the distillation zone and into the condenser. Thermocouple
3 (T
3
) was inserted from the bottom of the furnace and fitted on the outer wall surface of
the reactor, which measured the reactor outer wall surface temperature. As the
temperature gradient from the outer wall to the inner wall (3 mm thick) is insignificant,
the temperature measured by T
3
can be regarded as the temperature of the reactor inner
surface which is also close to the temperature of the feedstock in contact with the
reactor wall.

Figure 5-2 Scheme of the vertical pyrolysis apparatus

In the experiment apparatus, a M303PY Gallenkamp electronic furnace was used to heat
the reactor as an external heating resource. In the modified system, a 60 mm long
stainless steel pipe was placed beneath the reactor pipe thus the reactor is located at the
79
hottest position within the furnace. [12] In this way, char production is minimized by
avoiding the relatively slow pyrolysis in the low temperature zone. In addition, the
bottom empty 60 mm long pipe also reduced heat loss from the reactor.

In the experimental system, nitrogen bottle supplied the pure nitrogen to purge the air
out of the system before the experiment started. The condenser is a tube-shell heat
exchanger where the pyrolysis gases flew inside the tube and cooling water flew
between the tube and the shell. The cooling water was directly from tape at a
temperature of 10 to 15 C. The condenser was effective enough to drop the temperature
of the pyrolysis product to less than 30 C. The temperature in the laboratory room was
15 C. After the condenser, liquid and non-condensable gases were separated in a two-
way beaker in which the liquid was collected and weighed after each run of the
experiment. The non-condensable gases which were cooled down to less than 30 C in
the condenser were then collected by a water sealed cylinder which measured the
volume continuously during the experiment. After the experiment, the non-condensable
gases were collected by a balloon with an inner aluminium layer for gas analysis.

The non-condensable gases from the experiment were analysed using Agilent 3000A
Micro Gas Chromatography (Micro-GC) which has two columns (A and B), thus, two
streams of gases can be analysed simultaneously. (Figure 5-3) Column A used argon as
a carrier gas, which measured hydrogen and relatively heavy hydrocarbon gases. In
column B, helium was used as the carrier gas to measure nitrogen, oxygen, carbon
monoxide, carbon dioxide and methane.

Liquid products were analyzed using a Varian Gas Chromatography (GC) CP-3800.
(Figure 5-4) The column applied was a Varian CP-SIL capillary column of 15 mm long
and 0.32 mm in diameter with 1 m wall thickness and wax coating on the inner wall
surface. This column was able to identify hydrocarbons from C5 to C45. An alkane
standard mixture supplied by Sigma-Aldrich was used for the assay of the GCs
performance. The standard mixture contained all even n-alkanes from C10 to C40 with
80
50 mg/L in n-heptane. The liquid samples were also analyzed by using Gas
Chromatography-Mass Spectrometry (GC-MS) at Hill Laboratories, Hamilton, New
Zealand.

Figure 5-3 Agilent 3000A Micro Gas Chromatography

Figure 5-4 Varian Gas Chromatography CP-3800

Microstructure of the char produced from the plastic pyrolysis process was analyzed by
using JEOL JSM 7000F high resolution scanning electron microscope (SEM) at the
Department of Mechanical Engineering, University of Canterbury. (Figure 5-5) Element
analysis in the scanning electron microscope and electron microprobe is performed by
measuring the energy and the intensity distribution of the X-ray signal generated by a
focused electron beam. When the electrons strike the sample, a variety of signals are
81
generated, and it is the detection of specific signals which produces an image or a
sample's elemental composition. [110] Standardless ZAF method was applied for SEM-
EDS (scanning electron microscope and energy-dispersive x-ray spectrometer).

Figure 5-5 JEOL JSM 7000F high resolution scanning electron microscope
5.1.2. Experiment method
At the beginning of the experiment, 20 grams of the LDPE particles were weighed using
a four decimal place Mettler AE 200 balance and were filled into the pyrolysis reactor.
Then, the system was sealed and purged using the nitrogen gas for one minute to create
an oxygen free environment. After this, the furnace was turned on to full capacity with
control scale at 100, equivalent to heating power of 881 W. During the experiment,
three temperatures (T
1
, T
2
and T
3
) and the volume of the collected non-condensable
gases were recorded every minute until temperature T
3
rose above 800 C when no
product was left in the reactor. In order to investigate further cracking of the heavy
pyrolysis product, three lengths of the distillation pipes (380 mm, 280 mm and 200 mm)
were used separately in the experiments. The extra length above the furnace is cooled
by the ambient air. Longer length of the reactor pipe leads to higher efficiency of
condensation and higher reflux rate. In this section, only the results of high and low
82
reflux tests (using 380 mm and 200 mm distillation pipes) are reported while the effects
of the reflux distillation will be discussed in the following section.
The collected liquid, non-condensable gases and char were collected and analysed. The
non-condensable gases were analyzed by using Agilent 3000A Micro Gas
Chromatography (Micro GC). In the gas analysis, both of the columns A and B were set
at 90 C in the Micro GC. The injector temperature was set at 95 C. (Table 5-2) The
run time of column A is four minutes and that of column B is 10 minutes. This time
setting allows hydrocarbon gases with the retention time less than n-butane to come out,
such as hydrocarbons from C
1
to C
3
and butene and butane isomers. Some of the gases
were identified by running a gas standard with this method. (Table 5-3)
Table 5-2 Micro GC set points and configuration
Micro GC Setpoints A B
Sample Inlet Temperature (C) 95 95
Injector Temperature (C) 95 95
Column Temperature (C) 90 90
Sampling Time (s) 15 15
Inject Time (ms) 10 15
Run Time (s) 240 600
Post Run Time (s) 120 60
Pressure Equilibration Time (s) 15 60
Column Pressure (kPa) 206.8 137.5
Post Run Pressure (kPa) 275.8 137.5
Detector Filament Enabled Enabled
Detector Sensitivity Standard Standard
Detector Data Rate (Hz) 20 20
Baseline Offset (mV) 0 0
Backflush Time (s) 15.0 n/a
83
Table 5-2 Micro GC set points and configuration (Continued)
Injector Type Backflush Fixed Volume
Carrier Gas Argon Helium
Column Type
Molecular
Sieve
Plot Q
Detector Type TCD TCD
Inlet Type Heated Heated

Table 5-3 Calibration table
Peak Name Retention Time (min)
Hydrogen 0.462
Oxygen 0.610
Nitrogen 0.777
Methane 0.876
CO2 0.955
Ethene 1.099
Methane 1.139
Ethane 1.203
CO 1.340
propane 2.430
butane 7.561

The oils from low reflux rate process contained heavy molecular weight products and
formed yellow cream; while the oils from high reflux rate process was clear liquid.
(Figure 5-6) The cream product from low reflux rate process turned into clear liquid
84
when it was heated to 60C. The melted cream was able to be sucked by a one micro
litre GC syringe for GC CP-3800 analysis injection.

Figure 5-6 Oil product from low (left) and high (right) reflux processes.

In the liquid oil analysis, the liquid was firstly flash-vaporized at 320C when it was
injected into the GC. Then the vapour flew through the column which temperature was
initially controlled at 80C for two minutes. After this, the column temperature was
increased to 300C at a heating rate of 10C/min. The temperature remained at 300 C
until no further peaks were observed. The total analysis time for the high reflux liquid
product was 60 minutes and that for the low reflux product was 150 minutes. The GC
allowed the hydrocarbons with carbon number between 7 and 40 to be separated and
analyzed. In the analysis, the concentration of the liquid components was presented as
molar percentage.
Char from the LDPE pyrolysis were found at the bottom of the reactor, which were
black fine powder and particles. The char microstructure was analyzed by using the
JEOL JSM 7000F electron microscope.

In the experiments, HDPE was also used for pyrolysis; however, it was found that the
process and products from the HDPE pyrolysis were identical to those of LDPE
pyrolysis. Therefore, this thesis only presents the results of the LDPE pyrolysis.

85
Process analysis
During the pyrolysis experiments, the space temperature in the reactor (T
1
),

the reactor
outer wall surface temperature (T
3
) and the volume of the non-condensable gases were
recorded every minute and the results are shown in Figure 5-7 for LDPE and in Figure
5-8 for HDPE. Both figures show the pyrolysis with high reflux rates. From the results
of temperature profiles and non-condensable gas generation, the whole pyrolysis
process can be divided into three stages: initial heating up stage (initial 18 minutes), fast
pyrolysis stage (18 to 34 minutes) and decreasing pyrolysis stage (after 34 minutes). In
the heating up stage, the space temperature (T
3
) remained low until about 18 minutes
when no non-condensable gases were generated. However, the reactor wall temperature
continued increasing during the heating up stage.

After about 18 minutes, the generation of non-condensable gases increased dramatically
and the space temperature kept increasing. However, the temperature on the reactor wall
surface stopped rising one minute after the massive non-condensable gases produced
and then remained almost constant for about 16 minutes. As discussed in previous
chapters, the initial gas production rate indicates the random cracking in the early fast
pyrolysis stage. However, from the previous analysis, the energy required for the
cracking reaction is not large; therefore, significant amount of energy must have been
consumed in somewhere else as the reactor outer wall surface temperature remained
constant indicating constant heat transfer rate from the furnace to the reactor. In this
stage, the vapour from the primary cracking went up into the distillation zone, then,
were condensed and refluxed back to the pyrolysis zone. This process of condensation
and re-cracking consumed a significant amount of heat which was carried up by the
vapour from the pyrolysis zone to the distillation zone. Therefore, it has been observed
that reactor space temperature (T
1
) increased but reactor wall temperature (T
3
) remained
constant after 18 minutes from the start. Through this reflux process, low boiling point
products flew gradually into the condenser.

86
In the final termination pyrolysis stage, less vapour was produced and less energy was
required thus the reactor wall temperature (T
3
) started increasing again. The high
boiling point hydrocarbons were further pyrolyzed (secondary cracking) when the
reaction surface temperature rose above 500 C. This secondary cracking was indicated
through the second rapid increase on the gas production curve. (Figure 5-7) However,
the less high boiling point vapour was produced in this stage; the total vapour product
from the pyrolysis zone was reduced although the non-condensable gases kept
increasing as less condensate must have been generated at this time. This resulted in a
decrease in the reactor space temperature.

0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60 70
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.5
1
1.5
2
2.5
G
a
s

v
o
l
u
m
e

(
L
)
T1 space temperature T3 Surface temperature Gas volume

Figure 5-7 High reflux rate LDPE pyrolysis process

In the low reflux rate pyrolysis, the secondary cracking was less intensive than the high
reflux rate pyrolysis, thus higher boiling point hydrocarbons were generated as liquid
product. Higher boiling point hydrocarbons have higher viscosity than that of lower
boiling point hydrocarbons; [104] therefore, the viscosity of the liquid product from low
reflux rate process is higher. (Figure 5-6) the effect of reflux distillation on the product
distribution was further investigated in the following experiments. (Section 5.2)
87

0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60
Ti me (mi n)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.5
1
1.5
2
2.5
G
a
s

v
o
l
u
m
e

(
L
)
T1 space temperature T3 surface temperature gas volume

Figure 5-8 High reflux rate process pyrolysis on HDPE

The temperature profiles of high reflux rate HDPE process are listed in Figure 5-8.
There was no significant difference in the pyrolyzing process between HDPE and
LDPE. The temperature profile and non-condensable gas production are identical
between pyrolysis of LDPE and pyrolysis of HDPE indicating similar cracking
processes. Both of the LDPE and HDPE underwent secondary cracking when the low
boiling point hydrocarbons were removed. Because of the above similarity and the
higher value potential for recycled HDPE to be used in other products, LDPE is the
most suitable for energy production using the waste plastic stream. [7-8] Therefore,
LDPE was intensively studied in this study as a typical polyethylene material.

The results of product distribution of high reflux rate process LDPE pyrolysis are given
in Table 5-4 from the results, it can be seen that the conversion of LDPE to
hydrocarbons was over 99% and very little char was produced in the experiment as fine
black powers and particles found at the bottom of the reactor. The high reflux rate
88
process experiments were repeated five times. The 95% confidence interval of the
oil/wax mass was calculated, 1 . 0 7 . 16 g.

Table 5-4 Product distribution
LDPE HDPE
Product Mass (g) Percentage Mass (g) Percentage
Oil/wax 16.6 83% 16.7 83.5%
Char 0.04 < 1% 0.03 < 1%
Gas (estimated)* 3.4* 17% 3.3* 16 %
*Note: The volume of collected LDPE gas was 2.03 L. The average molecular weight
of the LDPE gases was calculated to be 38g/mol or 3.4g. The mass of HDPE gases was
calculated from the difference between the mass of the feedstock and the oil and char
products.

Non-condensable gas analysis
A typical Micro-GC analysis result for the non-condensable gases is shown in Figure
5-9 with the top chart from Column A and bottom chart from Column B. By integrating
each peak through the GC program, the composition of the corresponding gas species
was determined and the results from Figure 5-9 are given in Table 5-5. In Table 5-5,
Norm%' is the normal percentage of a component in the gas sample. From the above
results, it is known that the non-condensable gases consisted of oxygen (O
2
), nitrogen
(N
2
), methane (CH
4
), ethene (C
2
H
4
), ethane (C
2
H
6
), propane (C
3
H
8
), butane (C
4
H
10
) and
other four unidentified species (peak6, peak 8, peak 13 and peak 23). The oxygen,
carbon dioxide and some nitrogen gases were likely to be from contamination of air
during the gas sampling and sample collection process. The remaining nitrogen is
believed to be due to the purge gas left in the system. There were four peaks (peaks 6, 8,
13, and 23) in the GC analysis chart which needed to be identified from further analysis.
89
(Table 5-5, Figure 5-9) According to the result, methane, ethene, ethane, peak8,
propane, peak13, and butane are the major components in the non-condensable gases
from LDPE pyrolysis. The retention time of peak 8 was between propane and ethane;
therefore, peak 8 was believed to be propene. Peak 13 could be one of butene and
butane isomers, which would come out between propane and n-butane. [65] According
to liquid product analysis and other identified gas species, it was most likely to be 1-
butene because most of 1-alkene could be generated in the -scission reactions. [52, 83,
97] The 1-butene was also identified by other researchers. [32, 51, 58, 79, 83, 88, 111-
112] There was no H
2
detected in the gases. The hydrogen free radicals generated from
initiation reactions may combine with alkenes and saturate the carbon double bonds.
This has not been proven yet.

Table 5-5 Non-condensable gas analysis results for high reflux LDPE pyrolysis

90

Figure 5-9 Micro GC analysis chart for non-condensable gases from pyrolysis of LDPE with
high reflux rate; column A (top), column B (bottom)

The proportion of C
1,
C
2,
C
3,
and C
4
are 12.2%, 32.0%, 34.7%, and 21.1%; respectively.
44% of the gas products are n-alkane. The rest should be alkenes and alkane isomers.
The average molecular weight of the LDPE pyrolysis gases was calculated based on its
distribution. (Table 5-6) Therefore, the average molecular weight of the gas product is
38g/mol. The distribution of the gas product also varies with the variation of reaction
conditions. The difference of the gas products from the primary cracking and the
secondary cracking reaction was also investigated.

91
Table 5-6 Non-condensable gas distribution and its average molecular weight
Component Norm% Corrected
Carbon
number Percentage
Average
MW
Methane 6.53 12.2% C1 12.2% 16
Ethene 11.26 21.1%
C2 32.0% 29 Ethane 5.87 11.0%
peak6 0.70 1.3%
C3 34.7% 42*
peak7 0.12 0.2%
peak8 11.32 21.2%
Propane 6.42 12.0%
peak13 6.14 11.5%
C4 21.1% 56*
Butane 4.74 8.9%
peak23 0.38 0.7%
Total 100.0% 100.0% 38
*Note that: Peak8 and peak13 components are assumed to be propene and 1-butene,
respectively. Contaminated gases and very minor gas species are ignored.

Char product analysis
Char was analyzed through the JEOL JSM 7000F SEM-EDS in the Department of
Mechanical Engineering at University of Canterbury. The SEM image of the char is
shown in Figure 5-10 and the chemical elements in the char are given in Table 5-6. It
was found that the char contained 92.88% solid carbon, 6.18% oxygen, 0.86% calcium
and very tiny proportion of silica (0.08%). (Table 5-7) However, these values are only
used for indication due to the data scattering (R
2
=0.4474). This result was also in
consistent with the finding by Shah et al.. [42] From the SEM image, it can be observed
that the char particles were attached to each other and adhesion was formed with rough
surface. (Figure 5-10) The adhesion behaviour of the char particles at high temperature
92
could a potential problem for a continuous fix-bed reactor which would form fouling on
the reactor surface.

0.2 mm 0.2 mm 0.2 mm
0.2 mm 0.2 mm

Figure 5-10 Electron microscope photo of LDPE char surface

Table 5-7 ZAF Method Standardless Quantitative Analysis
Element (keV) mass% Error%
C 0.277 92.88 0.19
O 0.525 6.18 2.70
Si 1.739 0.08 0.82
Ca 3.690 0.86 1.89
Total 100.00
Note that: Fitting Coefficient 0.4474. The experimental error was significant; therefore,
these numbers are not accurate.
93
5.1.4. Identification of the components in liquid product
The viscosity and colour of the LDPE pyrolysis oil varied with the pyrolysis condition
as discussed in Section 5.1.2. It was clear yellow-brownish liquid from high reflux rate
process but became creamy solid wax with low reflux rate process. (Figure 5-6) In
analysis of the liquid product, a specially designed 1 l GC syringe was used to transfer
liquid product into the GC CP-3800. However, the syringe could only be used for liquid
but not for wax. Therefore, in order for the wax to be sampled by this syringe, the wax
was preheated to 60 C which turned into clear liquid for the GC analysis.
The GC analysis results for the LDPE pyrolysis liquid are shown in Figure 5-11 for high
reflux rate (top) and low reflux rate (bottom). In total, 115 hydrocarbons were found in
the high reflux process oil product and 121 peaks were detected in the low reflux rate
pyrolysis. (Figure 5-11) The components from both the high and the low reflux rate
processes had similar peak distribution in the first 60 minutes from the GC analysis. In
the liquid from low reflux rate pyrolysis, the final 6 liquid peaks are high boiling point
components (C
37
to

C
42
) which were not found in the high reflux process pyrolysis
liquid product.

Figure 5-11 Distribution of low (top) and high (bottom) reflux rate LDPE liquid pyrolysis
products
94

In the liquid product from the high reflux pyrolysis, the hydrocarbons chains ranged
from C
5
to C
36
but those from the low reflux rate pyrolysis ranged from C
5
to C
42+
.
These results are in agreement with other studies. [18, 20, 27, 37, 49, 58, 60, 63, 86, 89,
98, 101, 103-106] Lee and Shin [50] found that the distribution of the oil product
molecular weight ranges up to 500 which corresponds to C
40.
The molecular weight of
the major components is between 200 and 400, which is from C
14
up to C
30.
Aguado et
al. [29] found that the carbon chain length in the products is up to C
55.

From Figure 5-12, the components appeared on the GC analysis chart as peaks in sub-
groups. Each sub-group consisted of a small peak in the front and two major peaks
behind. (Figure 5-11) According to the literature review [28, 31, 87], the small peak in
the front of each group is , -dialkene. The following two peaks are 1-alkene and n-
alkane, respectively, according to other studies. [58] This chromatogram obtained in
this study is very similar to those obtained by other researchers. [27, 59, 88, 111-115]
The oil products from both processes (high reflux and low reflux rate pyrolysis) had a
normal distribution with the maximum peak value at the 13.4 minute (C
14
group).
However, liquid from the high reflux rate pyrolysis contained lower proportion of the
hydrocarbons with carbon chain length greater than 14 than that from the low reflux rate
pyrolysis. On the other hand, the liquid from the high reflux rate pyrolysis contained
lighter molecular weight hydrocarbons with carbon chain number less than 14 compared
to that from the low reflux pyrolysis. (Figure 5-11) The heavy hydrocarbons with
carbon number greater than 36 do not appear in the high reflux process product. This
was due to the effect of secondary cracking of the liquid products, which was caused by
the difference of reflux rates in the pyrolysis.
In order to identify the two major components in each sub-group, the liquid oil
generated from the LDPE pyrolysis was firstly diluted in n-hexane with a ratio of
1:1000. Then, 1% v/v 1-Cetene (1-C
16
) and 1% v/v n-Cetane (n-C
16
) were added into
the diluted oil, respectively. The GC results for these new samples are shown in Figure
5-12 with comparison with the only diluted oil. In theory, by adding known components
in the liquid, the GC chromatogram will show a clear increase for the peaks of added
95
components. On the word, the increased peaks are the known components. From the
results shown in Figure 5-12, 1-C
16
and n-C
16
were identified on the sample GC analysis
graph, which appeared at the 16
th
minute on the graph. The C
16
group is the group with a
clearly increased peak in the graph. (Figure 5-12 middle and bottom graphs) Therefore,
it is determined that the front major peak in the group is 1-alkene and the second major
peak is n-alkane. This technique was applied on all groups in the LDPE liquid product
and thus the corresponding hydrocarbons were identified.

Figure 5-12 Comparison of LDPE liquid sample (top) and the liquid with additive 1-C
16

(middle) and n-C
16
(bottom)

Once a specific carbon number is known (C
16
), other hydrocarbons with different
carbon numbers can be determined by comparing the LDPE sample with a standard
hydrocarbon mixture that consisted of even carbon number n-alkane from C
10
to C
40
.
(Figure 5-13 middle graph) Each component in the hydrocarbon standard was 50mg and
diluted in n-heptane to 10ml. The correspondent even carbon number n-alkane peaks
were increased when the LDPE product was mixed with the standard. (Figure 5-13
bottom graph) Therefore, the increased peaks were the even carbon number n-alkanes.
As the increased peak at the 16
th
minute was initially identified to be n-C
16.
, other peaks
were thus determined based on these two experimental results.
96

Figure 5-13 Comparison of LDPE liquid sample (top) and hydrocarbon standards (middle and
bottom)

The liquid sample was also analyzed by GC-MS. The results from the GC-MS analysis
clearly illustrated the carbon number in each hydrocarbon group. (Figure 5-14)
However, it did not separate the 1-alkene and the n-alkane peaks adequately. The
hydrocarbons with significant concentration were detected up to C
30
in the solution. The
carbon number of each group is shown in Figure 5-14. The result on the individual
component was not applied because the 1-alkene and the n-alkane peaks were
overlapping each other.

97

Figure 5-14 GC-MS analysis on LDPE sample diluted in n-pentane

5.1.5. Conclusions
PE is one of the most commonly used plastic materials. According to the pyrolysis
processes and the product distribution, there is no significant difference between LDPE
and HDPE, therefore, LDPE was extensively investigated and reported in this chapter of
the thesis. The LDPE products consist of non-condensable gases, liquid or wax
hydrocarbons, and char. The proportion of each product can be changed by changing the
reaction conditions.

From this study, it is found that the product distribution was significantly influenced by
reflux rate in the pyrolysis process. The products consisted of 83% oil/wax, 16% of
non-condensable gases, and less than 1% char with high reflux rate pyrolysis. In the
high reflux rate pyrolysis, heavy molecular weight hydrocarbons were refluxed into the
pyrolysis zone and were further pyrolyzed into lighter hydrocarbons such as non-
condensable gases and light liquid oil. Intensive secondary pyrolysis reaction was
observed in the high reflux rate process. The char product was largely solid carbon with
a small proportion of silica and calcium oxides.

98
The non-condensable gases (C
1
to C
4
), oil and wax (C
5+
) were analysed to be
hydrocarbons with carbon chain number ranged from C
1
to C
42+
. The hydrocarbons with
the same carbon chain number were grouped together on the chromatogram and the
highest concentration for the liquid product had a peak value of at the C
14
group. (Figure
5-11) In order to determine the sub-group peaks, an innovative method was developed
by diluting the sample and adding standard liquid with known carbon numbers. It was
identified that the front major peak is 1-alkene and the other major peak is n-alkane in
each group, respectively.

The influence of reflux rate on the products is very significant. In the high reflux rate
pyrolysis, hydrocarbons above C
36
were further pyrolyzed thus was not found in the
liquid product. However, a significant amount of heavy hydrocarbons above C
36
were
found the in the low reflux rate pyrolysis. The components in the liquid were also
analyzed though GC-MS but the GC-MS method could not distinguish individual peaks
in each sub-group. The effects of reflux rate and secondary cracking reactions on the
products were further investigated in the following section.

99
5.2. Effects of reflux distillation
Based on the previous experiments, it was found that the reflux distillation has
significant effect on the pyrolysis process and the products. Secondary cracking
reactions on the heavy molecular weight hydrocarbons occurred when light
hydrocarbons were removed from the pyrolysis reactor. These reactions converted the
proportion of heavy molecular weight hydrocarbons into light molecular weight
hydrocarbons. The effect of different reflux rates on the product and the process was
further investigated in this series of experiments.

5.2.1. Experiments
The material used in this experiment was also virgin LDPE particles which were the
same as the material specified in the previous section. (Section 5.1.1) The pyrolysis
apparatus was also the same as used in Section 5.1. (Figure 5-2) Three different lengths
of pyrolysis pipes, 200 mm 280 mm, and 380 mm, were applied in these experiments,
representing low, medium and high reflux rates, respectively. In each experiment run,
20 grams LDPE was placed in the pipes at the beginning and the same experimental
procedures as described in the previous section were followed. In the experiment, the
temperatures in the reactor space (T
1
), at outlet of the distillation pipe of the entrance of
the condenser (T
2
) and at the reactor wall outer surface (T
3
). The non-condensable gas
volume was measured during the experiment and collected after the experiment. Liquid
product and char were also collected after each run of the experiment. The products of
gas and liquid were analysed using the same methods as described in Section 5.1.1. .
5.2.2. Result and discussion
Effects of reflux rate on the pyrolysis process
For understanding of the pyrolysis process, temperatures at outer surface of the reactor
wall (T
3
) were firstly examined for high reflux rate, low reflux rate and for empty
reactor run when the pyrolysis apparatus was tested without plastic in it. As discussed
previously, the outer surface temperature (T
3
) is close to the inner surface temperature
thus it indicates the temperature profile of the internal reaction surface of the pyrolysis
100
reactor. The T
3
profile measured with the empty reactor can be used as a baseline of the
temperature change to examine the effect of the filled plastics and reflux rate on the
pyrolysis process as shown in Figure 5-15. From the profiles of T
3
of baseline, and
pyrolysis with low and high reflux rates, it is found that these profiles were almost the
same in the first 16 minutes from the start when the wall temperatures reached
approximately 450C. This result confirms that the heat consumed in this initial period
was only for heating up of the reactor and the furnace and that the pyrolysis reaction
had not occurred. However, after the 16
th
minutes, the T
3
profiles with LDPE in the
reactor increased slower than the baseline, indicating the pyrolysis started occurring.
This was apparent for the high reflux rate pyrolysis in which the wall temperature
almost remained constant at 470 C. When the wall temperatures rose to 500C, they
increased further at similar rate at the baseline.

0
100
200
300
400
500
600
700
0 10 20 30 40 50
Ti me (min)
P
y
r
o
l
y
s
i
s

s
u
r
f
a
c
e

t
e
m
p
e
r
a
t
u
r
e

(
C
)
Baseline temperature Low reflux ratio pyrolysis High reflux ratio pyrolysis

Figure 5-15 Profiles of outer wall surface temperatures with empty reactor and during LDPE
pyrolysis with low and high reflux rates

For the low reflux rate pyrolysis, the wall temperature was only one minute apart from
the baseline after the pyrolysis started; indicating that only the heat transferred in the
101
one minute was needed for the plastic pyrolysis reactions. From this finding, the energy
consumed during the one minute can be calculated as the energy required for LDPE
pyrolysis reactions including plastic cracking, vaporization and energy loss in reflux
distillation. However, the pyrolysis with high reflux rate took much longer time and
required more energy due to secondary cracking and heat loss in the distillation.
According to the energy balance calculation in section 3.2.2 (Table 3-6 and equation
18), the energy required for LDPE pyrolysis and vaporization process is calculated in
Table 5-8.

Table 5-8 Energy balance of the 20g LDPE pyrolysis and vaporization
20g LDPE C
3
H
6
1-C
8
H
16
1-C
16
H
32
1-C
28
H
56
Total
Hr, kJ/mol 23.00 23.00 23.00 23.00
H, kJ/mol 24.12 72.32 163.34 304.12
H
v
, kJ/mol - 33.76 50.42 - 181

Low reflux products 7% 22% 50% 21% 100%
mol of component 0.033 0.039 0.044 0.011 0.128
Energy required kJ 1.57 5.09 10.51 3.54 20.71

High reflux products 15% 31% 44% 11% 100%
mol of component 0.072 0.055 0.039 0.005 0.171
Energy required, kJ 3.39 7.08 9.22 1.77 21.45
Note: H
r
is the reaction enthalpy, which is calculated in Section 3.2.2; H is the
energy that increased the temperature of material from the initial status, T
1,
to the final
product status, T
2
; H
v
is the vaporization heat of each component.
102

According to the results given in Table 5-8, the theoretical energy consumption for
pyrolysis of the 20g LDPE varied from 20.71kJ for low reflux rate to 21.45kJ for high
reflux rate based on product distribution.

The above theoretical energy consumption can be compared to the actual energy
consumption based on the reactor outer wall temperatures. In the experiments, the total
energy consumed consisted of both the energy for LDPE pyrolysis, vaporization, and
the energy loss from reflux distillation. The output power of the furnace was 881 W.
The difference between baseline curve and those of LDPE pyrolysis was used for
determination of the energy consumption in the LDPE pyrolysis which is equal to the
product of the furnace output power and the time difference to reach the same
temperature by the end of the pyrolysis. As an example, the energy calculations for the
low and the high reflux rate pyrolysis are listed below in which E
low
is the energy
requirement for low reflux rate and E
high
is the energy requirement for the high reflux
distillation. P is the power of the furnace.

kJ J W t t P E
baseline low low
86 . 52 sec 60 sec / 881 min 1 881 ) ( = = = =

kJ J W t t P E
baseline high high
04 . 740 sec 60 14 sec / 881 min 14 881 ) ( = = = =

From the theoretical energy demand for the pyrolysis and the actual energy consumed in
the experiment, the heat loss can be calculated. For example, in the low reflux rate
pyrolysis, the energy lost was kJ kJ kJ 15 . 32 71 . 20 86 . 52 = . Hence, 60.8 percent of the
total energy was consumed in the low reflux rate distillation process. In the high reflux
rate process, the total energy consumed was the energy provided in 14 minutes or740kJ
in total, in which only 21.45 kJ was consumed by the pyrolysis. Therefore, 97% of the
total energy consumed was lost in the high reflux rate pyrolysis. The energy
103
consumption for the pyrolysis including vaporization and secondary cracking was only
3% of the total energy consumed in this case.

Secondary cracking of the primary hydrocarbon products was the major reactions
during the high and medium reflux rate pyrolysis processes. The secondary cracking
reduces the heavy molecular weight hydrocarbons to light molecular weight
hydrocarbons thus producing more non-condensable gases. From the analysis of
pyrolysis process, it is also known that the initiation reactions consist of random and
end chain cracking on the polymer carbon chains, which also produce light hydrocarbon
products, such as non-condensable gases. [33, 52, 77, 94-95, 100, 116-118] As
mentioned in Section 3.1, the production rate of non-condensable gases is a sensitive
indicator for the initiation reactions. This analysis can be confirmed by the experimental
results of the non-condensable gas production rates as shown in Figure 5-16 for high
flux rate pyrolysis, in Figure 5-18 for medium reflux rate pyrolysis and Figure 5-20 for
low reflux rate pyrolysis. In the low reflux rate pyrolysis, only one peak was found for
the non-condensable gas production at the early stage of the pyrolysis but there were
two peaks for the medium and high reflux rate pyrolysis. In the latter two cases, the first
peak was similar to that in the low reflux rate pyrolysis but the second peak appeared
later in the process.

The above process can also be understood from the measured temperature in the reactor
space (T
1
). After about16 minutes from the start, the LDPE particles were pyrolyzed
quickly and the product vapour rose into the distillation zone. Therefore the space
temperature (T
1
) increased rapidly. After four minutes rapid increase, the gas production
slowed down, which was a sign of the primary initiation reaction completing. In high
and medium reflux rate pyrolysis, most of the heavy molecular weight hydrocarbons
were refluxed back to the pyrolysis zone for further cracking at the same time when the
product vapour rose to the distillation zone. (Figure 5-2) The light molecular weight
product vapour generated from the secondary cracking then flew out of the distillation
zone, and condensed and collected.

104
0
50
100
150
200
250
300
350
400
0 10 20 30 40 50 60
Tim e (m in)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.05
0.1
0.15
0.2
0.25
0.3
G
a
s

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
L
/
m
i
n
)
T1 T2 gas production rate

1
), outlet temperature from distillation
zone (T
2
) and non-condensable gas production for high reflux rate LDPE pyrolysis process

T
2
is the measured temperature at the exit of distillation pipe, which did not change
unless the hot product vapour passed through the exit. Due to the fast heat loss from the
distillation pipe, T
2
was also affected by the temperature of the product vapour. During
the primary pyrolysis process, T
2
did not change instantly with the production of non-
condensable gases and the increase of distillation space temperature T
1
because most of
the hydrocarbons were refluxed back to the pyrolysis zone before reaching the exit
point. In this case, the non-condensable gas was not sufficiently hot and the flow was
not sufficiently high for T
2
to be increased. This can be confirmed by the observation
that the liquid product was only formed when T
2
started increasing.

For the high reflux rate pyrolysis, the reactor space temperature (T
1
) started to increase
sharply from 16
th
minute and remained relatively stable at 300-350C until 33 minutes
from the start of the experiment. The relatively stable temperature was caused by the
significant reflux of the primary products. According to the gas production rate, the
effect of secondary cracking was not significant. The change of the vapour temperature
was negligible in the reflux distillation zone. (Figure 5-17) However, the outlet
105
temperature (T
2
) increased during this period, which indicates the increase of the high
temperature products passing through the exit pipe. Some of the vapour passing through
was condensed to form liquid product and the rest remained as non-condensable gases
collected. Those products were the light hydrocarbons from the primary cracking.

After about 33 minutes, the pyrolysis was almost completed and no more heavy
hydrocarbons were produced and refluxed back to the reactor, therefore, no more
product vapour past the exit pipe. Hence, both T
1
and T
2
dropped towards the baseline
temperature. (Figure 5-16 and Figure 5-17)

0
100
200
300
400
0 10 20 30 40 50 60
Reacti on Ti me (mi n)
S
p
a
c
e

t
e
m
p
e
r
a
t
u
r
e

(
C
)
T1 Baseline T1

Figure 5-17 Profiles of space temperature, T
1,
from the distillation pipe during the high flux
rate pyrolysis of LDPE with comparison with baseline

The profiles of temperatures T
1
and T
2
in the medium reflux rate pyrolysis are to those
of the high reflux rate pyrolysis as discussed before. (Figure 5-18) However, the interval
(7 minutes) of the two peaks for the non-condensable gas production, representing the
primary and the secondary pyrolysis was much less than that in the high reflux rate
pyrolysis (14 minutes). With shorter length for the distillation pipe in the medium reflux
106
rate pyrolysis, light products were easier to be removed compared to the high reflux rate
pyrolysis. Small amount of char was found at the top of the pyrolysis zone after the high
reflux rate process. This indicates that the secondary crackings occurred there when the
reflux product flew back to the pyrolysis zone.

0
50
100
150
200
250
300
350
400
450
0 10 20 30 40 50 60
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.05
0.1
0.15
0.2
0.25
0.3
G
a
s
p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
L
/
m
i
n
)
T1 T2 Gas production rate

1
zone (T
2
) and gas production for medium reflux rate LDPE pyrolysis

In the low reflux rate pyrolysis, the reflux effect was very minor during the process as
almost all the distillation pipe was covered by the furnace. Therefore, secondary
cracking peak was not observed on the non-condensable gas production rate curve.
(Figure 5-19) The primary pyrolysis product vapour, once produced, was removed
quickly from the reactor. The heavy molecular weight hydrocarbons were condensed in
the condenser. Some wax solidified in the water cooled condenser. Some products were
left in the system. This is considered as the reason of the pyrolysis product loss in the
material mass balance calculations.

107
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.05
0.1
0.15
0.2
0.25
0.3
G
a
s

p
r
o
d
u
c
t
i
o
n

(
L
/
m
i
n
)

1
zone (T
2
) and gas production for low reflux rate LDPE pyrolysis

Effects of reflux rate on the product distribution
From the above discussion, reflux rate has a significant effect on the LDPE pyrolysis
process and also on the product distribution. This has been noticed in previous plastics
pyrolysis kinetic studies. [31, 46, 49, 58, 68, 79, 99, 112-113, 115, 117] However, due
to the complexity of the products, no report has been found on the identification of
individual carbon numbers of the hydrocarbon products. The quantification of the effect
of secondary cracking on the product distribution has not been found in the literature
review.

The product distribution for the LDPE pyrolysis with low, medium and high reflux rates
are given in Table 5-9. In the table, the values were corrected with consideration of
material loss such as wax sticking in the condenser. The proportion of the char was
found to be less than 0.5% in any cases studied; therefore, the ahs was ignored in the
material balance calculations. From the table, it is known that the liquid/wax products
108
were 93.1% for the low reflux rate pyrolysis but this was reduced to 83.3% for the
medium reflux rate pyrolysis and to 81.8% for the high reflux rate pyrolysis.
Correspondingly, the non-condensable gas proportion was increased from 6.9% in the
low reflux rate pyrolysis to 16.7% and 18.3% in the medium and high reflux rate
pyrolysis, respectively.

This clearly demonstrates that in the medium and high reflux rate pyrolysis, some of the
heavy hydrocarbons in the primary cracking liquid product were converted into non-
condensable gases through the reflux distillation. Although char content was not
presented, it was found in the final products in the form of mainly fine black carbons
attached on the reaction surface at the bottom of the reactor. Some char was also found
in the pyrolysis zone in both high and medium reflux rate processes. The location of
char formation may be regarded as an indicator for locations where cracking reactions
had occurred in the pyrolysis. From this hypothesis, the primary cracking reactions
occurred at the bottom of the reactor, and the secondary cracking reactions occurred on
the wall of the pyrolysis zone where the condensed hydrocarbons were refluxed back to
the reactor.

Table 5-9 Product distribution from LDPE pyrolysis with different reflux rates
20g LDPE Reflux rate in pyrolysis process
Product Low Med High
Gas (C1~C4) 6.9% 16.7% 18.3%
Liquid (C5+) 93.1% 83.3% 81.7%
Char* - - -

Non-condensable gas product
109
In this study, the non-condensable gases generated from the initial primary cracking and
from the secondary cracking were collected and analysed separately. (Table 5-9) The
conversion of PE into non-condensable gases has a positive relationship with reflux
rate. Thus, the proportion of the gases reveals the level of secondary crackings because
there is large amount of the gases produced in the random crackings of the refluxed
heavy hydrocarbons. The results are given in Table 5-10. As far as the author is aware,
this approach is the first in this area of studies.

Table 5-10 Product distribution in non-condensable gas components from primary and
secondary cracking processes
Primary gas product Secondary gas product
Component
Product
group Norm% Percentage
Average
MW Norm% Percentage
Average
MW
Methane C1 12.2% 12.2% 16 11.0% 11.0% 16
Ethene
C2
21.1%
32.0% 29
12.0%
27.7% 29 Ethane 11.0% 15.7%
peak6
C3
1.3%
34.7% 42
0.6%
41.9% 42
peak7 0.2% 0.3%
Propene 21.2% 22.5%
Propane 12.0% 18.5%
peak13
C4
11.5%
21.1% 56
9.4%
19.2% 56
Butane 8.9% 9.1%
peak23 0.7% 0.7%
Total 100.0% 100.0% 37.6 100% 100.0% 38.2
110
From the results, it is found that the non-condensable gases were all hydrocarbons from
C
1
to C
4.
The interference of purging gas, nitrogen, has been eliminated in the
normalized proportion of the gas components and most of the major components have
been identified in the analysis as given in Table 5-10. Peak 13 was not identified but is
supposed to be one of butene or butane isomers according to its retention time. Based
on the analysis results, the average molecular weight of the non-condensable gases was
calculated to be 37.6 and 38.2 g/mol for the primary and the secondary cracking
processes, respectively.

Although the major non-condensable gas components from the two cracking processes
were the same, the proportions of each individual gas components were different. The
proportion of ethene from the secondary cracking (12%) was only about half of that
from the primary cracking process (21.2%). However, the proportion of ethane and
propane from the secondary cracking were, respectively, 43% and 54% higher than
those from the primary cracking. Other gas components (methane, propene) had similar
proportions between these two cracking processes. Overall, the proportion of the alkene
decreased from 60% in the primary cracking gases to 45% in the secondary cracking
gases.

0%
5%
10%
15%
20%
25%
methane ethene ethane peak6 peak7 propene propane peak13 butane peak23
P
e
r
c
e
n
t
a
g
e

o
f

c
o
m
p
o
n
e
n
t
primary pyrolysis gases secondary pyrolysis gases

Figure 5-20 Distribution of the non-condensable gas components from the primary and the
secondary cracking in the LDPE pyrolysis
111

Liquid and wax products
From the results presented in previous section, it is known that with high and medium
reflux rates, the proportion of non-condensable gases were significantly increased and
correspondingly, the heavier hydrocarbons (C
12+
) were decreased. The results of the
liquids and non-condensable gases from the high and low reflux rate pyrolysis of LDPE
are given in Figure 5-20. From the table, the proportion of the heaviest hydrocarbon
group (C
29+
) was most reduced from 9.8% at low reflux rate to 1% at high reflux rate.
Therefore, the primary hydrocarbon product with higher molecular weight was likely to
be cracked in the secondary cracking process. (Table 5-11) The distribution of the final
product can be significantly changed by adjusting the reflux rate in the distillation
process.

Table 5-11 Distribution of liquid and non-condensable gas products from different reflux rate
pyrolysis processes
Hydrocarbon group
low reflux process product
proportion w/w
high reflux process
product proportion w/w
C
1
~C
4
7% 18.3%
C
5
~C
11
17.0% 29.5%
C
12
~C
16
36.0% 32.8%
C
17
~C
20
18.8% 10.8%
C
21
~C
28
11.4% 7.5%
C
29+
9.8% 1.0%

Further analysis revealed that the secondary cracking has different effects on alkanes
and alkenes in each group with the same carbon chain number. Previous GC analyses
results show that in each sub-group, n-alkane, 1-alkene, and , -dialkene were the
major components. By comparing the GC results between the liquid products from low
reflux rate pyrolysis and those from the high reflux rate pyrolysis (Figure 5-21), the
112
proportion of , -dialkene, that appeared as small peaks in the front of each sub-group
for the low reflux rate pyrolysis, was greatly decreased to a very low level in the high
reflux rate pyrolysis products. (Figure 5-21) Correspondingly, the 1-alkene and n-alkane
peaks from 5 minutes to 15 minutes were significantly increased in the high reflux rate
pyrolysis products. Obviously, the difference of the height of 1-alkenes and that of n-
alkane peaks was reduced in the high reflux rate pyrolysis products. As a result, the
ratio of 1-alkene to n-alkane decreased after the secondary cracking. Particularly, the
reduction on the 1-alkene/n-alkane ratio was more significant in the heavy molecular
weight hydrocarbons than the light hydrocarbons. For example, the ratio of 1-C
15
/n-C
15

dropped from 1.2 to 1, while the ratio of 1-C
24
/n-C
24
dropped from 1 to 0.4. (Figure
5-21) Therefore, the secondary cracking cracked more 1-alkenes than n-alkanes,
particularly, heavy molecular weight 1-alkenes. The hydrogen free radicals may react
with 1-alkenes and produced n-alkanes. These are not found in any other relevant
research reports.

Figure 5-21 Comparison of pyrolysis liquid components between low reflux rate (top) and high
reflux rate (bottom)
Note that: The scale of Y axis for the two charts is not the same.
113

Char product
Neither high nor low reflux process pyrolysis produced significant amount of char. The
mass/mass proportion of char content in both processes was less than 0.5 percent. The
amount of char was neglected in the analysis.

5.2.3. Conclusions
Secondary cracking in high and medium reflux rate pyrolysis has significant effects on
the pyrolysis process and distribution of the pyrolysis products. However, the secondary
cracking was not obvious in the low reflux rate pyrolysis. In the pyrolysis with reflux,
majority of the energy consumed was lost in the reflux distillation process, accounting
for 73% and 99%in the low and the high reflux rate pyrolysis, respectively.

With high and medium rate pyrolysis, a large amount of heavy molecular weight
hydrocarbons were further cracked into non-condensable gases and lighter
hydrocarbons through the secondary cracking. As a result, the conversion of non-
condensable gases indicates the reflux rate or the level of the secondary crackings. The
proportion of the non-condensable gases increased from 6.9% from the low reflux rate
pyrolysis to 18.3% from the high reflux rate pyrolysis. The wax content (C
29+
)
decreased from 9.8% to 1% correspondingly. It is also found that in each carbon
number sub-group, the 1-alkenes were more likely to be cracked than were the n-
alkanes, particularly in the heavy molecular weight products. The percentage of , -
dialkenes was significantly decrease after the secondary cracking. The char content in
every process remained below 0.5% w/w, which did not change much with the reflux
rate and was negligible in the analysis.
114
5.3. Catalytic Pyrolysis on Low Density Polyethylene
5.3.1. Materials and equipment
Catalytic pyrolysis was studied previously and the published results show that catalyst
can change the reaction process and the distribution of pyrolysis products, particularly,
for PE that produced high molecular weight products in pyrolysis. [29, 56, 64, 119] As
the proportion of wax (heavy molecular weight hydrocarbons) is high in the PE
pyrolysis products, catalytic pyrolysis was investigated to convert the wax into diesel
range fuels rather than use high reflux rate distillation that consumes a large amount of
energy. According to previous studies (Section 2.1.5), pore size and the ratio of Si/Al
are the two key factors determining the effect of zeolite catalyst because zeolites are
crystalline micro-porous aluminosilicates. [70-71, 75]

In this study, the catalysts used in the experiment were provided by Nankai University
Catalyst Co. Ltd., China. In order to maximize the diesel range and other liquid product
and to reduce the proportion of wax, three types of catalysts, NKC-5 (ZSM-5), NKC-7
(NaY), and NKC-3A zeolite were investigated. The physical appearance of these
catalysts is shown in Figure 5-22. The pyrolysis apparatus used for LDPE pyrolysis was
also used in the catalytic pyrolysis experiments. (Figure 5-2)

(a) (b) (c)
Figure 5-22 Catalyst appearance: (a) NKC-3A, (b) NKC-5, and (c) NKC-7

115
The catalyst of NKC-3A zeolite mainly consists of alkali metals and silica aluminate,
which adsorbs molecules with certain range diameters no larger than 3A (0.3 nm). The
NKC-3A zeolite catalyst is widely used in petroleum processing for gas cracking, which
can adsorb water molecules while excluding hydrocarbon molecules. [120] In the
experiment, the effects of the zeolite with different pore sizes on the pyrolysis product
were examined.

The catalyst NKC-5 is ZSM-5 zeolite based catalysts with the ratio of Si/Al at 25 and
pore size of 0.5 nm. NKC-5 is used for converting hydrocarbons such as C
5
(alkene or
alkane) into aromatics like benzene, toluene, xylene, etc. [121] The NKC-5 performance
was tested by the manufacturer in a continuous fixed bed reactor with catalyst to
feedstock ratio of 1:10. The results showed a conversion efficiency of 99% with gas
yield of 31.3% and aromatic compound of 62%. [121] In this study, the NKC-5 was
used to maximize the petrol range product or aromatics in the LDPE pyrolysis.

NKC-7 is an alkali metal silica aluminate based catalyst with NaY zeolite structure. The
NaY zeolite can adsorb the molecules of certain range of diameter no larger than
1nm.[122] NKC-7 is a catalyst for cracking the heavy molecular weight hydrocarbons
into lighter hydrocarbons during diesel production.

5.3.2. Experimental
In order to investigate the effects of catalyst on the pyrolysis products, lower reflux rate
pyrolysis of LDPE was conducted. The results from experiments using the three
catalysts were compared with the results of matching pyrolysis experiments without
catalysts. (Section 5.2) In this way, the effect of catalyst on heavy molecular weight
hydrocarbons was identified.

116
Four runs of pyrolysis experiment were conducted at low reflux rate: Run 1 (control)
was pyrolysis of LDPE without any catalyst, Runs 2 to 4 were pyrolysis, respectively,
with catalysts of NKC-5, NKC-7 and NKC-3A. In each run, 20 g LDPE was used and in
Runs 2 to 4 2g catalysts was added.

In Runs 2 to 4, the LDPE was first placed in the pyrolysis reactor then, the catalyst was
added into the reactor before the experiment started. The following procedures,
measurements and product analysis methods were the same as those of the low reflux
rate pyrolysis experiments described in Section 5.1.2.

The pyrolysis products measured in the experiments are given in Table 5-12 for the
contents of non-condensable gases and liquids. The char content was also lower than
0.5% thus it was not included in the product analysis. In the table, the results are mass
proportion in the product. The mass proportion of the non-condensable gases was
calculated from values measured gas and the estimated average molecular weight of the
gases.

Table 5-12 Pyrolysis product distribution w/w with catalytic and comparison with that
without catalysts pyrolysis
Gas Liquid
No catalyst 17% 83%
NKC-7 25% 75%
NKC-5 58% 42%
NKC-3A 24% 76%
117
From the product analysis results, it is found that the effect of the catalysts on the
distribution of the pyrolysis product was significant. All of the three types of catalysts
tested promoted the production of non-condensable gases and reduced the proportion
liquid product. (Table 5-12)

The catalysis of NKC-5 had the most significant effect on the gas production with the
proportion of the non-condensable gases increased from 17% to 58%. In addition, it was
also observed that the liquid product from NKC-5 catalytic pyrolysis had relatively low
viscosity while the liquid products from other runs (Run1, Run 3 and Run4) were
creamy solid wax at ambient temperature (20C). The other two types of catalysts
(NKC-7 and NKC-3A) also increased the production of non-condensable gases but with
mush less extent from 17% to 25% and 24%, respectively. Obviously, NKC-5 is the
most effective catalyst examined for dewaxing and increasing the production of non-
condensable gases.

The profiles of non-condensable gas production during four runs of LDPE pyrolysis are
presented in Figure 5-23. The starting point of the pyrolysis can also be observed from
the gas production curves in which the pyrolysis reactions started at the same time (17
min) in Run 1 (control), Run2 (NKC-7) and Run 3 started at the same elapsed time.
Therefore, the profiles of reactor outer wall temperature (T
3
), reactor space temperature
(T
1
) and outlet temperature from the distillation pipe were the same for these three runs.

However; in Run 4 where NKC- 3A was used, the non-condensable gas was generated
at 15 minute from the start, 2 minutes earlier than other runs. Form the temperature
profiles presented earlier, the heating up rate for the system was 30 C/minute with no
difference for baseline run or for runs with catalysts. From this observation, it is
concluded that the primary cracking temperature for the pyrolysis with NKC-3 catalysts
was reduced by 60 C to 390 C due to the effect of the added catalyst (NKC-3A).

118
0
1
2
3
4
5
6
0 5 10 15 20 25 30 35 40
Ti me (mi n)
G
a
s

v
o
l
u
m
e

(
L
)
NKC-7 NKC-5 NKC-3A No catalyst

Figure 5-23 Gas production of LDPE catalytic pyrolysis

In the experiments with catalysts, it was found that the catalysts remained at the bottom
of the reactor after the experiment but these catalyst particles turned into black after the
reactions. It is believed that this colour change was mainly caused by the fine carbon
residues left on the catalysts.

The liquid products were analyzed using GC as described before and the results are
shown in Figure 5-24 in which the order of chromatographs from the top to bottom are
for Run 1 (control), Run2 (with catalyst NKC-3A), Run 3 (NKC-5) and Run 4 (NKC-7),
respectively. From these results, it is seen that the three types of catalysts had different
influence on the composition of the liquid product. The quantitative results for the
liquid products in each run are given in Table 5-13.

119

Figure 5-24 GC analysis results for the liquid products from pyrolysis of LDPE
Chromatographs from top to bottom are respectively: Run 1 (control), Run 2 (NKC-3A), Run 3
(NKC-5) and Run 4 (NKC-7)
Note: The scales are different for the graphs.

From the results in Table 5-13, it is found that in the LDPE pyrolysis using catalyst of
NKC-3A (Run 2), the heavy molecular weight hydrocarbons (C
28+
) has decreased from
6% in the control to 1% while the diesel range product (C
11
-C
27
, New Zealand winter
diesel from Mobil measured by Feng Gao) also had a significant decrease from 66% in
the control to 37%. Additionally, from the GC chromatographs, the height of first peak
in each hydrocarbon sub-group, 1-alkenes, was also significantly reduced compared to
the n-alkanes, the second peak in the same sub-groups. On the other hand, the
percentage of the LPG (C
1
-C
4
) and the petrol (C
5
-C
10
) range hydrocarbons has increased
from 17% to 24%, and from 11% to 37%, respectively.

120
In Run 3 with catalysts NKC-5, the diesel and the wax range products were greatly
reduced compared to the control. The LPG gas product increased from 17% to 58% and
the petrol range product increased from 11% to 18%. (Table 5-13) The dewaxing effect
of NKC-5 on the pyrolysis of LDPE is very significant. However, the structures of the
components have also been changed with the NKC-5 catalyst which is reflected by the
flat and irregular peaks GC chromatograph. (Figure 5-24) The concentration of the 1-
alkenes and the n-alkanes was greatly reduced. A few aromatic compounds, benzene,
toluene, and xylene, were significant in the liquid product. Further analysis shows that
the concentrations of benzene, toluene, and xylene were 3.8%, 9.4%, and 5.6%;
respectively. Therefore, the catalyst of NKC-5 has remarkable effect on converting
straight chain hydrocarbons into aromatics and promoting LDPE pyrolysis gases. The
results from this study are consistent with previous report of Uemichi, et al., who tested
the catalysts of zeolite ZSM-5. [62]

In Run 4 where catalyst NKC-7 was used, the diesel range product was significantly
reduced from 66% in the control to 37%. (Table 5-13) However, the proportions of
other hydrocarbons were all increased to a certain extent, including wax being increased
from 6% to 14%, petrol range being increased from 11% to 24% and LPG gas from
17% to 25%. The overall composition of the NKC-7 liquid pyrolysis product was
similar to that of the control except for higher proportion of petrol and wax range
products. The GC chromatograph for the NKC-7 liquid pyrolysis products was similar
to that of the control (Figure 5-24) where 1-alkenes and n-alkanes were the dominant
components in the liquid.
Table 5-13 Product distribution of catalytic pyrolysis of LDPE and comparison with control
Product distribution C1-C4 C5-C10 C11-C27 C28+
No catalyst 17 11 66 6
NKC-3A 24 37 37 1
NKC-5 58 18 22 2
NKC-7 25 24 37 14
Commercial fuel range LPG Petrol Diesel Wax
121

5.3.4. Conclusions
The effects of three types of zeolite based catalysts (NKC-3A, NKC-5, NKC-7) were
investigated in this experiment on LDPE pyrolysis. The catalysts NKC-5 and NKC-7
did not affect the start of pyrolysis reactions compared to the control, but the pyrolysis
reactions using catalyst NKC-3A started 2 minutes earlier controlled to the control, thus
it is concluded that the cracking temperature was decreased by 60C from 450 C to 390
C with catalyst NKC-3A.

All of the catalysts tested have promoted the proportion of non-condensable gases
significantly. The catalyst NKC-5 has the most significant impact with the gas
production being increased from 17% in the control to 58%. The other two catalysts,
NKC-3A and NKC-7, promoted the proportion of non-condensable gases to 24% and
25%, respectively.

The diesel and the wax range products were reduced in the LDPE pyrolysis using both
NKC-3A and NKC-5. However, the wax range product using NKC-7 was increased
from 6% in the control to 14%. By using the catalyst NKC-5, the 1-alkenes
hydrocarbons were significantly reduced in the carbon chain sub-group. NKC-5 assisted
to convert most 1-alkenes and n-alkanes into aromatics (toluene, benzene, and xylene)
in the liquid product of LDPE pyrolysis. Catalysts have significant effects on the
product distribution and the pyrolysis process. However, the use of catalyst may include
other issues like changing catalyst, loss of catalyst activity, etc.. This is depended on the
reactor and the type of catalyst.
122
6. Pyrolysis of PP, PS and Plastic Mixtures
6.1. Pyrolysis of Polypropylene
This part of study investigated the pyrolysis process and products using virgin
polypropylene (PP) with trade brand of AR564 in order to maintain the consistency of
the material. The virgin PP is in the form of oval particles with dimensions of 3 mm by
4 mm as shown in Figure 6-1. Other properties of the virgin PP are listed in Table 6-1.

Figure 6-1 Appearance of virgin PP (AR564) used in this study

Table 6-1 Thermal and physical properties of virgin PP using in this study
Properties Unit Value ASTM method
Melt flow rate g/10 min 24 D1238
Melting point C 160-165 -
Density g/cm3 0.90 D792
123

This study also used the vertical batch pyrolysis apparatus which was used in Section 5.
(Figure 5-2) In order to investigate the effect of reflux rate, three lengths of the reactor
pipe were used (200 mm, 280 mm and 380 mm), which corresponded to low, medium
and high reflux rates for the distillation. In a similar way to Chapter 5, water sealed
cylinder was used to measure the volume of non-condensable gases generated. A
balloon with an aluminium inner layer was used to collect the gas samples for analysis
using the same 3000A Micro GC as that in the previous experiments described in
Section 5.2. The liquid product was collected and analyzed with the same Varian Gas
Chromatography CP-3800 as that used in Section 5.2.

6.1.2. Experimental
Before the experiment, 20g virgin PP was placed in the reactor. Then, nitrogen gas was
used to purge the air out of the apparatus for one minute. After that, the M303PY
Gallenkamp electronic furnace was turned on with the power load setting at 100 which
corresponds to 881 W. The experiment stopped when no products were further
collected. The objectives of part of study were to examine the process and products of
PP pyrolysis and to compare with those of LDPE pyrolysis thus the main part of the
experiments were conduced using the reactor length of 280 mm or the medium reflux
rate pyrolysis. High and low reflux rate processes were also tested to investigate the
effect of reflux rate on the products. For the detailed operation procedure and product
analysis (gas and liquid), please refer to Section 5.2. The char content in this study was
also very low thus no analysis was undertaken.

Process Analysis
In a similar way as the pyrolysis of LDPE, the PP pyrolysis produced liquid and non-
condensable gases. The reflux rate in the distillation process also had significant effects
on the PP pyrolysis process and products. The liquid product collected after the
124
condenser was yellow creamy wax with low reflux rate PP pyrolysis, while it was clear
yellow-brown oil from medium or high reflux rate PP pyrolysis.

Figures 6-2 and 6-3 show the profiles of reactor space temperature (T
1
), temperature at
the reactor outer wall surface (T
3
) and the production rate of the non-condensable gases.
Figure 6-2 is for the medium reflux rate pyrolysis and Figure 6-3 is for the high reflux
rate. From the result of medium reflux rate pyrolysis (Figure 6-2), only a single stage of
fast production of non-condensable gas which started 17 minutes from the beginning of
the pyrolysis process. This is different from the pyrolysis of LDPE at the medium reflux
rate. (Figure 5-18) The starting point for the non-condensable gas production indicates
the starting time of the pyrolysis reactions. In the medium reflux rate process, the
refluxing distillation time was only three minutes. Therefore, the two rapid increase
period of non-condensable gases production were merged together. (Figure 6-3)

However, the PP pyrolysis with high reflux rate showed a second fast rate of non-
condensable gas production after about 30 minutes which is similar to the LDPE
pyrolysis (Figure 5-16) although the second fast production rate for the PP pyrolysis
was less than that of the LDPE pyrolysis at the high reflux rates. These above
observations may indicate that PP pyrolysis had less reflux using the same length of the
reactor pipe as less condensable gas was generated from the secondary cracking
process. This can be further confirmed by comparing the product distribution at the
same reflux rate between pyrolysis of LDPE (Table 5-9) and pyrolysis of PP. (Table 6-
2)

The pyrolysis process can be better understood by analysing the measured temperatures
at the reactor outer wall surface and in the rector space. (Figures 6-2 and 6-3) From the
temperature profiles at high reflux rate pyrolysis, it is found that the reactor outer wall
surface temperature (T
3
) increased continuously from the start and remained at about
450 C when the massive non-condensable gases were generated. This lasted about 13
minutes during which the gas production was gradually decreased. (Figure 6-3) During
125
this period, intensive reflux distillation occurred and the refluxed products consumed
significant amount of heat thus maintaining the reactor temperature relatively constant.
When the products were gradually removed, the temperature of T
3
increased again at
about 30 minutes from the start and in the meantime more non-condensable gases were
generated again, mainly from the secondary cracking. It is observed that the temperature
reached 510C when the secondary cracking started. The reactor wall surface
temperature eventually reached about 700C at the end of the pyrolysis.

The PP pyrolysis with medium and low reflux rates had similar temperature profiles but
the second increase in the non-condensable gas production rate was not observed due to
the lack of secondary cracking.

0
100
200
300
400
500
600
700
800
900
0 10 20 30 40
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.05
0.1
0.15
0.2
0.25
0.3
G
a
s

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
L
/
m
i
n
u
t
e
)
T1 T3 T2 Gas production rate

Figure 6-2 Profiles of medium reflux rate PP pyrolysis
126
0
100
200
300
400
500
600
700
800
900
0 5 10 15 20 25 30 35 40
Ti me (mi n)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
G
a
s

p
r
o
d
u
c
t
i
o
n

r
a
t
e

(
L
/
m
i
n
)

Figure 6-3 Profiles of high reflux rate PP pyrolysis

In the PP pyrolysis, non-condensable gases, liquid and char were collected and the
results for the high reflux rate pyrolysis are given in Table 6-2. The char content was
insignificant, less than 0.05g. The char was fine black power attaching on the inner
surface of the pyrolysis zone. Hence, the mass of the char was hardly to be precisely
quantified.
Table 6-2 Products from PP high reflux rate pyrolysis
Product Gas (C
1
~ C
4
) Liquid (C
5+
) char
Collected values 1.91 L 16.63 g -
Calculated and
corrected values
3.13g* 16.83g** Less than 0.05
Proportion 15.7% 84.2% Less than 0.25%
Note: * The mass of non-condensable gases was calculated from the measured gas
volume and the calculated average molecular weight of the gases. (Table 6-3)
** The 1% mass loss in the products from 20g PP, 0.2g, was assumed to be the residue
liquid attached on the wall in the apparatus.
127

From the gas analysis, the composition of the non-condensable gases was determined
and the results are illustrated in Figure 6-4 for medium reflux rate PP pyrolysis. From
the results, it was found that there were seven main components in the gases which had
concentration greater than 1%. The highest concentration component is propene which
accounted for 44% in the total non-condensable gas product. Other significant gas
components include methane (11%), ethene (10%), ethane (12%) and another
unidentified one at peak 28. There was 4% hydrogen detected in the gases, which did
not appear in the LDPE pyrolysis products. The identified peak 28 was located between
propane and n-butane; therefore, it can be one of the butane isomers or butenes
according to other studies. [34, 101]

0%
10%
20%
30%
40%
50%
H
y
d
r
o
g
e
n
M
e
t
h
a
n
e
E
t
h
e
n
e
E
t
h
a
n
e
P
e
a
k

6
P
e
a
k

7
P
r
o
p
e
n
e
P
r
o
p
a
n
e
P
e
a
k

1
2
P
e
a
k

2
8
P
e
a
k

2
9
B
u
t
a
n
e
P
e
a
k

2
3

Figure 6-4 Components in non-condensable gas from PP pyrolysis

The proportion of each component is affected by the reflux rate and operation
conditions (temperature and pressure). From previous studies, it is known that at a
relatively low temperature, C
1
to C
4
are the main components. [47] Hydrogen gas is also
128
produced from PP pyrolysis while it was not found in the non-condensable gases from
PE pyrolysis. Methane and ethylene are the main components in a high temperature PP
pyrolysis. The pyrolysis experiment conducted in this study was a relatively low
temperature process and the gas product composition results are similar to the reported
gas results of PP pyrolysis at 400C. [21, 23, 61, 112]

Table 6-3 Distribution of non-condensable gases from PP pyrolysis
Compound Percentage Expected MW
Hydrogen 4.09% 2
Methane 11.11% 16
Ethene 9.69% 28
Ethane 12.49% 30
Peak 6 0.53% 42
Peak 7 0.64% 42
Propene 43.79% 42
Propane 3.81% 44
Peak 12 0.32% 56
Peak 28 11.76% 56
Peak 29 0.79% 56
Butane 0.82% 58
Peak 23 0.16% 70
MW avg 100.00% 36.7
Note: MW means molecular weight;
MW avg means average molecular weight of the gases

129
Assuming that peak 28 was one of the isomers of butane, the average molecular weight
of PP pyrolysis non-condensable gases was calculated to be 36.7 g/mol. This is slightly
lower than the average molecular weight of the gases from LDPE pyrolysis, 38 g/mol,
(Table 5-6) because the proportion of C
3
and C
4
in PP non-condensable gases is less
than that in LDPE gases. It is possibly due to the difference between the molecule
structure of PP and PE. Different from the long chain hydrocarbons from random
cracking of PE, initial cracking on the PP carbon chain likely occurs on the C-C bond
attached to the tertiary carbons. The free radicals with methyl- side group that did not
combine with other free radical groups formed propene. Thus, 44% of propene was
found in the gases, which is much higher than that in PE and PS. The volume of the
collected gases was 1.91 L. Therefore, the mass of the non-condensable gases is 3.13
grams. (Table 6-2)

Liquid product
The liquid from high and medium reflux rate PP pyrolysis processes was yellow-brown
oils at medium reflux rate which was similar to PE pyrolysis oils. (Figure 6-5) The
condensed product from low reflux rate process was yellow creamy wax that was also
similar to that from LDPE low reflux rate pyrolysis. The liquid product was analyzed
through GC and GC-MS and the results from the medium reflux rate pyrolysis of PP are
shown in Figure 6-6. The GC chromatograph of PP pyrolysis oil has methyl-side groups
on the carbon backbone which is different from that of the LDPE pyrolysis oil. As
mentioned in the previously, in the tertiary carbons, the joints with methyl groups have
the weakest C-C bonds which will break first in the initiation reactions. (Section 3.1.2)
During pyrolysis, the free radicals with methyl groups combined together with each
other at the ends formed many oligomers of propene. In the pyrolysis of PP, the
intramolecular radical transfer is preferred to the intermolecular one in the PP pyrolysis
process. Thus, the low oligomers predominate in the PP pyrolysis oil is more volatile
than that of PE. [68] The difference between the PE pyrolysis oil and the PP pyrolysis
oil can be observed on the GC analysis graphs. (Figure 5-11 and Figure 6-6)

130
(a) (b) (c)
Figure 6-5 Comparison of liquid oil from PP pyrolysis at high (a), medium (b), and low (c)
reflux rates processes

Figure 6-6 GC analysis result of PP pyrolysis oil with medium reflux rate

A similar pyrolysis product distribution to that of this study was also observed by other
researchers (Figure 6-7) who found that the product distribution of PP pyrolysis is
developed by a free radical mechanism. [123-124] When PP is pyrolyzed at about 400
C, propene gas were eluted and collected in the process. There were 99 peaks detected
from the GC analysis in which the main oligomers of propene are dimers, trimers,
131
tetramers, and pentamers of propene in the first 13 minutes, which accounts for 68% of
the concentration of liquid products. Both GC chromatographs (Figure 6-6 and Figure
6-7) show an outstanding high peak at 4.2 minutes and other significant peaks in the
first 20 minutes, which accounts for 81% v/v of the total liquid product. The
outstanding peak at the 4.2 minute was identified as 1, 3, 5 - trimethyl - cyclohexane
(C
9
H
18
). This cyclohexane accounts for 21% in the liquid products. The peaks came out
after the 13
th
minute were heavy boiling range oligomers, a series of which are , -
isodialkenes. Others can be isoalkanes and 1-isoalkenes. [68]

Figure 6-7 Py-GC-MS chromatogram of isotactic PP at 500 C [68]
Note that: P
n
in the GC chromatograph denotes oligomers of n propene unites. Peaks
labelled * are dialkenes.

The isoalkanoic structure of PP is retained in its pyrolysis products. Therefore, the
octane number of PP pyrolysis oil might be higher than other straight chain oil products
such as oils from PE pyrolysis. [86, 125]
132
In the PP pyrolysis, very little char was produced which was also found to be fine black
powder attaching on the wall in the reactor pipe as found in the PE pyrolysis. The
amount of char was insignificant thus ignored in the product analysis.

6.1.4. Conclusions
In the PP pyrolysis, the pyrolysis reactions started at a similar temperature as that of PE
of 450 C. In the non-condensable gas product of PP pyrolysis, there were 96%
hydrocarbons and 4% hydrogen. Propene accounted for 44% and dominated in the
gases.

It is believed that the methyl side group in PP structure is the main reason for high
proportion of oligomers of propene in the PP pyrolysis oil products. Based on the
analysis of PP pyrolysis liquid, 99 components were found in which 1, 3, 5 - trimethyl -
cyclohexane (C
9
H
18
), oligomers with 3 propene units, is one of the most dominant
components, which accounts for 21% in the liquid products. The low molecular weight
oligomers with 2 to 5 propene units (first 13 minutes in GC graph Figure 6-6) accounted
for 68% of the total liquid product. The components after the 13
th
minute were high
molecular weight oligomers, in which series of isoalkanes, 1-isoalkenes, and , -
isodialkenes are the major components. However, the products from PE pyrolysis are
straight chain hydrocarbons, 1-alkenes, n-alkanes, and , -dialkenes. No significant
amount of isomers was found in the PE product because of the difference between the
chemical structure of PP and PE.

133
6.2. Pyrolysis of Polystyrene
6.2.1. Materials
There are many types of polystyrene (PS) materials. One of the popular types is high
impact polystyrene (HIPS) and thus in this part of study, the virgin HIPS 486B was
used as the pyrolysis material in order to maintain consistency. The HIPS 486B is in the
form of white oval particles with dimensions of 3 mm x 2 mm (Figure 6-8) and its
properties are given in Table 6-4. It is suitable for packaging as sheet application or
other applications where high impact strength and rigidity are required.

Figure 6-8 HIPS 486B sample

Table 6-4 The properties of HIPS 486B
Item Unit HIPS 486B ASTM method
Melt flow index (200/5) g/10 min 2.5 D1238
Melting point C 200 220 -
Density g/cm
3
1.05 D792
134
6.2.2. Experimental
The experiment apparatus used in this part of study was described in Section 5.1.1. In
this experiment, 20 g HIPS 486B was placed in the reactor before the experiment
started. After this, the apparatus was purged with nitrogen gas for one minute and then
the M303PY Gallenkamp electronic furnace was turned on to full scale of 100 power
load. As mentioned previous section, three lengths of the reactor pipe were used (200
mm, 280 mm and 380 mm), which corresponded to low, medium and high reflux rates
for the distillation. The results from medium reflux rate pyrolysis will be discussed in
more details in next section except that the effect of the reflux rate is discussed.

When vapour was produced, it was cooled down in the condenser from which the liquid
oil and non-condensable gas were separated and collected separated. For each condition,
two duplicate runs were conducted; one for measurement of gas volume production rate
and one for gas collection for analysis. Once there was no further vapour coming out
from the reactor, the experiment was completed when the reactor outer wall surface
temperature reached above 700 C.

As described in previous sections, the non-condensable gas product was analyzed
through 3000A Micro GC and the liquid pyrolysis product was analyzed through GC
and GCMS. In the liquid analysis, pure styrene diluted into n-hexane in a ratio of 1:100
was applied as a standard to identify the produced styrene in the HIPS pyrolysis liquid.
In the pyrolysis of PS, the char content was significant. The elements in the char
product were analyzed through the JEOL JSM 7000F high resolution scanning electron
microscope.

Pyrolysis Process Analysis
135
The measured temperatures at the reactor outer wall surface (T
3
) and in the reactor
space (T
1
) as well and the accumulated non-condensable gas volume are shown in
Figure 6-9 during the PS pyrolysis with medium reflux rate. From the results, it was
found that the non-condensable gases started to be produced at the 14
th
minute, a similar
time as the pyrolysis of LDPE and PP. (Figure 6-9) At that time, the pyrolysis reactions
of HIPS 486B started. The wall temperature T
3
at this time was 320 C which, unlike
the pyrolysis of LDPE and PP, continued increasing although a brief plateau was
noticed at the temperature of 400C. The temperature when the gas started to be
produced is close to the temperature from other studies which means that the cracking
temperature of PS is lower than that of PE pyrolysis. [106] This is attributed to the side
group of benzene in the polystyrene which is illustrated as follows.
.

The benzene side group reduced the stability of C-C bond in the PS polymer compared
with polymers with -H or -CH
3
side groups. Hence, the activation energy of PS
pyrolysis is lower than that of PP and PE.[34]

After the start of the pyrolysis reactions at 14 minutes, more non-condensable gases
were produced quickly which lasted about 17 minutes until 31 minutes and at that time
the major reactions were completed. There was no secondary cracking for gas
production appeared from the experimental results and this applied also to both high and
low reflux rate distillation pyrolysis experiments. Therefore, in the PS pyrolysis, the
primary cracking is dominant and all of the products were generated from the primary
pyrolysis. Reflux rate has insignificant effect on the process and the pyrolysis products.
This behaviour of the PS pyrolysis was not found in the literature review and is different
from the pyrolysis of PE and PP.
136

0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
G
a
s

v
o
l
u
m
e

(
L
)
T1 T3 Gas production

Figure 6-9 Profiles of reactor outer wall surface temperature, space temperature in the
reactor and the accumulated volume of the non-condensable gas in the PS pyrolysis with medium
reflux rate

Product distribution Analysis
In PS pyrolysis with medium reflux rate, liquid product was found to be clear red-brown
oils. (Figure 6-10) It is interesting to note that the liquid oil appearance did not change
much with the reflux rate. In the chemical analysis of the liquid oil, 52 components
were detected which were much less than those of PE pyrolysis liquid or PP pyrolysis
liquid. It was found that styrene was the dominant component in the pyrolysis liquid
that accounts for 68.6% v/v of the total liquid product.(Figure 6-13) This finding was
consistent with to the results of McCaffery and other researchers. [108, 117-118] In
different studies, the yield of styrene varies from 50% to 79%. [11-12, 21, 24-25, 34,
37, 106, 114, 126] This variation is likely to be due to differences in pyrolysis
conditions. Based on the above discussion, one of the major cracking reactions in the PS
pyrolysis is the chain strip cracking in which side functional group (styrene monomer)
broke off from the carbon backbone, forming the major component in the liquid
product.
137

From previous analysis on the PE pyrolysis reactions, it has been known that products
(including gas and liquid) from the random cracking should distribute continuously
from low molecular weight product to high molecular weight products. However, the
distribution of the PS pyrolysis products was not continuous. There were only six major
components in the liquid products (over 1% v/v). Styrene is from the chain strip
cracking. Others are mainly from end chain crackings but not from random
crackings.[127] During the pyrolysis, polystyrene was cracked into styrene, non-
condensable gases and other light aromatics in the primary cracking. From the
discussion in last section, the temperature profiles and non-condensable gas production
confirmed that there was no significant secondary cracking occurred on the primary
pyrolysis products. Therefore, the PS pyrolysis products were mainly formed during the
primary reactions. The proportions of non-condensable gases, liquid oil and char are
given in Table 6-4 which shows majority of the products is liquid (93%) with much less
gas (4%). However, compared to PE and PP pyrolysis, the char content in the PS
pyrolysis was much higher (3%). The char was black chips accumulated on the wall of
the pyrolysis zone.

Figure 6-10 Liquid product from PS pyrolysis with medium reflux rate
Table 6-5 Distribution of PS pyrolysis products
Product Gas (C
1
~ C
4
) Liquid (C
5+
) Char
Collected value 0.64 L 18.59 g 0.6 g
Corrected value (g) 0.81* 18.59 0.61
Proportion 4% 93% 3%
138
Note: * The mass of non-condensable gases was calculated from the measured gas
volume and the calculated average molecular weight of the gases.

The volume of non-condensable gas from the PS pyrolysis PS was much less than that
of the pyrolysis of HDPE, LDPE and PP as shown in Figure 6-11. The total non-
condensable gas from the high reflux rate pyrolysis of 20g PE and 20g PP was 2L
which accounted for 16.7% for PE (Table 5-9) and 15.7% for PP (Table 6-2) in the total
products. However, for the same material (20g) in the PS pyrolysis, only 0.64L gas was
collected and this accounted for 4% of the total products. (Table 6-5) Williams also
reported similar findings in his research. [24] Theses differences in the gas production
between different types of plastics are the results of different primary cracking process.
[83, 94, 97, 106]

0
0.5
1
1.5
2
2.5
0 10 20 30 40 50 60
time (min)
V
o
l
u
m
e

(
L
)
PS HDPE LDPE PP

Figure 6-11 Non-condensable gas production from pyrolysis of of PS, HDPE, LDPE, and PP at
medium reflux rate
The results from the GC analysis of PS pyrolysis gas are presented in Figure 6-12 which
shows six major components with corresponding proportion greater than 5%. (The
139
highest concentration gas component was methane (21%) followed by hydrogen (19%),
ethene (17%), propene (16%), unidentified component at peak 13 (13.5%) and ethane
(6%). The concentration of the hydrogen gas was the highest in all investigated plastic
types. It was also found the concentration of the alkenes was higher than that of the
alkanes. Ethene was 3 times as much as ethane. Propene was 11 times as much as
propane. Peak 13 was one of the unidentified components. According to its retention
time, it could be butene or butane isomer. The overall low proportion of the non-
condensable gas and the gas component concentration could be attributed to the
operation temperature and the structure of the PS. The results found from this study are
similar to those reported by other studies although there are some variations among the
reported values. [21, 84, 117-119]
0%
5%
10%
15%
20%
25%
H
y
d
r
o
g
e
n
M
e
t
h
a
n
e
E
t
h
e
n
e
E
t
h
a
n
e
P
e
a
k
6
P
r
o
p
e
n
e
P
r
o
p
a
n
e
P
e
a
k
1
3
P
e
a
k
2
6
B
u
t
a
n
e
P
e
a
k
2
3

Figure 6-12 Composition of PS pyrolysis gases with medium reflux rate
Liquid product
As discussed earlier, the liquid product from PS pyrolysis was the highest (93%) in all
of the three types of plastics (PE, PP and PS). (Table 6-5) The GC chromatograph of the
PS pyrolysis oil is shown in Figure 6-13 from which it can be seen that there were much
less components in the liquid than in the liquids produced from PE pyrolysis and PP
pyrolysis. Styrene is a dominant peak that accounts for 68.9% of the liquid. Kaminsky
et al. reported that in the liquid product from PS pyrolysis in a fluidised bed reactor,
140
styrene concentration was 64.9% of the feedstock mass..[20] Because the breaking off
of the styrene side groups from the carbon backbone of the polystyrene is the major
reaction in the PS pyrolysis, it is not surprising that the styrene is the main component
in the product. [35, 96, 108, 117-119, 121] In order to confirm this hypothesis and
findings in previous studies, a styrene standard was used in this study to identify this
outstanding peak in the GC analysis graph following the same procedure as discussed in
identifying liquid component in PE pyrolysis liquid. (see Section 5.1.4) This is
illustrated in Figure 6-14.

Figure 6-13 GC chromatograph in analysis of PS liquid pyrolysis product

Figure 6-14 Comparison of styrene standard (bottom graph) and polystyrene liquid product
(top graph)
141
Note: Top graph: polystyrene pyrolysis liquid in n-hexane with concentration of 1:100 ;
bottom graph: styrene in n-hexane with concentration of 1:100.
Based on the comparison of the styrene standard and PS pyrolysis liquid as shown in
Figure 6-14, it is further confirmed that the highest concentration component in the PS
pyrolysis liquid was indeed the styrene. A similar GC analysis result was reported with
all six major components identified by William. [25] Other major five components with
concentration over 1% in this research, which were assumed to be the same components
as Williams GC analysis results. (Table 6-6) The main components in the PS pyrolysis
liquid are styrene and other aromatics.

Table 6-6 Major components in the PS pyrolysis liquid
Peak
number
Component Concentration % Time (Peak on GC chromatograph)
(min)
2 Benzene 8.24% 3.157
3 Toluene 2.93% 4.487
4 Styrene 68.59% 5.011
5 Trimethlybenzene 7.51% 6.475
21 Styrene dimer 2.77% 16.912
26 Phenanthrene 1.98% 17.765
Total 92.02%

Char product
The char was found at the bottom and on the wall in the pyrolysis zone in the reactor
where the pyrolysis reaction occurred. No char was found in the transition area between
distillation zone and pyrolysis zone which further confirmed that the PS reflux products
142
would not be further cracked in the distillation like PE or PP. The proportion of char
from PS pyrolysis was 3%, which is much higher than that from PE and PP pyrolysis
(less than 0.5%). The appearance of the char from PS pyrolysis was also different from
that in the PE or PP pyrolysis. The char from the PS pyrolysis was 1 mm x 1 mm black
chips with metallic shine on their smooth surfaces. The element in the char was
analyzed with a scanning electron microscope (SEM) as shown in Figure 6-15. The
analysis results based on ZAF standard are given in Table 6-7. The PS pyrolysis char
consisted of only carbon (96.61%) and oxygen (3.39%).

Figure 6-15 SEM image of the surfaces of PS pyrolysis char

Table 6-7 ZAF Method Standard less Quantitative Analysis
Element (keV) Mass (%) Error (%)
C 0.277 96.61 0.18
O 0.525 3.39 2.80
Total 100.00

143
6.2.4. Conclusions
In the PS pyrolysis, the side group of polystyrene has very significant effects on the
pyrolysis process and the products. The side group, styrene monomer, reduces the
cracking temperature at the start point to about 320 C. Chain strip cracking is the main
reaction in the initial reactions. As a result, the yield of styrene is 63.8 % w/w of the
total feedstock. Different from PE and PP pyrolysis, reflux distillation has insignificant
effect on the PS product distribution because the molecular weight of the primary
products is relatively light. The percentage of non-condensable gases, oils and char is
4%, 93% and 3%; respectively. The composition of the gases consisted of 19%
hydrogen, and other hydrocarbon gases. The liquid contained 68.6% styrene, and other
aromatics. The elements found in the char are mainly pure carbon with a small amount
of oxygen.

144
6.3. Pyrolysis of the virgin and the post-consumed plastic
mixture
This part of the study aimed at the conversion of waste plastic into diesel or other fuels
through pyrolysis. Thus, pyrolysis experiments of post-consumed plastics were
conducted using post-consumed plastics provided by Green Fuel Technologies Ltd.
(Figure 6-16) The post-consumed plastics were plastic chips with a mixture of 50% PE,
25% PP, and 25% PS. The plastic chips were pre-washed but tags and labels were not
removed from the plastics, which would have some influence on the pyrolysis process
and the products.

Figure 6-16 Post-consumer plastic mixture of PE, PP, and PS

For comparison purposes, mixed virgin plastics with 25% of HDPE, LDPE, PP, and PS
each were also pyrolyzed using the same apparatus as used in the post-consumer
plastics. The properties of the virgin plastics were illustrated in the previous sections.
Thus, the interaction between PE, PP, and PS in the pyrolysis reactions can be revealed.
The effect of the contamination of post-consumer plastics was also investigated.

145
The pyrolysis apparatus used were the same one used in the previous experiments.
(Figure 5-2) In this part of study, the longest reactor pipe (380 mm) was applied in order
to achieve the best quality of liquid oil due to the secondary cracking of the PE and PP
primary products. The Micro GC and the GC CP-3800 with the same analysis program
were used to analyze non-condensable gases and liquid oils.

6.3.2. Experimental
There were two runs of the experiments, one for post-consumer plastic mixture and one
for virgin plastic mixture. Both of the virgin and the post-consumer plastic went through
the same pyrolysis process. In each run, 20 gram samples were placed in the 380 mm
long reactor pipe first before the experiment started. Then the system was purged by
nitrogen gas. After that, the furnace was turned on at full power load at scale of 100
which was equivalent to 881 W. During the experiment, the temperature of the reactor
outer wall surface (T
3
) and the temperature in the reactor space (T
1
) as well as the non-
condensable gas volume were recorded every one minute since the power was on. The
experiment was stopped 60 minutes after the start, at which time no further products
came out and T
3
was above 800 C.

The non-condensable gas and the liquid products were collected and analyzed
separately. The liquid was analyzed using GC and GC-MS to investigate the
components.

From analysis of the experimental results, it was found that the temperature profiles and
the gas production curve in the pyrolysis of the mixed post-consumer plastics were
similar to those of the pyrolysis of mixed virgin plastics due to the dominant PE (50%)
in both cased. This can clearly be seen from the comparison of the experimental results
of pyrolysis of virgin LDPE (Figure 5-8) and those of pyrolysis of mixed post-consumer
plastics. (Figure 6-17) It can be observed that in both cases, the gas production had two
146
fast production stages, one after about 18mintes and one after 32 minutes. The first one
corresponded the primary cracking and the second one corresponded to the secondary
cracking of the dominant feedstock, PE. However, in pyrolysis of mixed post-consumer
plastics, there was another small peak in the gas production at about 18 minutes which
was the gas production from PS pyrolysis. It is most interesting to note from the
pyrolysis of mixed plastics that there was a reduction in reactor wall surface
temperature (T
3
) after the small peak in the gas production. This is the evidence that the
primary cracking temperature of the PS is lower than that of PE and PP.
0
200
400
600
800
1000
0 10 20 30 40 50 60
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
G
a
s

v
o
l
u
m
e

(
L
)
T1 T3 Gas volume

Figure 6-17 Profiles of T
1,
T
3,
and non-condensable gas production in the pyrolysis of post-
consumer plastic mixture

The liquid product from pyrolysis of mixed plastic mixture was analyzed through GC
and the results are shown in Figure 6-18. Although the composition of the product from
the pyrolysis of mixed plastics is complex, it was found that most of the peaks present
in the mixture product could be identified form the individual plastic pyrolysis products.
(Figure 6-18) However, the peaks in the pyrolysis of mixed plastics are more plat
without any single outstanding peak observed. The major components from individual
plastic pyrolysis like 1-alkene and n-alkane groups from PE pyrolysis and aromatics
from PS still remained high concentration in the mixture product.
147

The components in the liquid product from post-consumer and virgin plastic mixtures
were very similar as shown in the bottom two graphs in Figure 6-18. The percentage of
each component varied slightly but not significantly. In both cases (mixed post-
consumer plastics and mixed virgin plastics) styrene was identified as the dominant
component in the liquid products with corresponding concentration of the styrene being
23.5% and 45.9%, respectively. The difference could be due to the difference of the PS
proportion in the post-consumer plastic mixture as this was supplied from industry.
Although the PS proportion was 25% in the bag supplied, there could be a higher
percentage of PS in the tested samples for the post-consumer plastic mixture. The
proportion of PS in the mixed virgin plastics was more reliable as the test mixture was
prepared by mixing required masses from each type, 25% PS in the tested virgin plastic
mixture.

Based on the results from the pyrolysis of mixed virgin plastics, the percentage of
styrene in the total product was 19.3%, which was derived from the chain strip reaction
of PS. This was calculated from GC analysis result (23.5% of the liquid product from
virgin plastic mixture) and the final product distribution (82% liquid product in Table
6-8). The conversion was then calculated to be 77.1%, which is higher than that in
pyrolysis of pure PS (63.8%). Therefore, the interaction among the different type of
plastics promoted the conversion of styrene in the PS pyrolysis.

148

Figure 6-18 Liquid products from individual and mixture of plastics pyrolysis
In the figure, the top graphs are for virgin PE, virgin PS and virgin PP. The bottom two
are for mixed post-consumer plastics (second from bottom) and mixed virgin plastics
(bottom).

From the gas production in pyrolysis of individual plastics (Figure 6-11), the expected
gas volume was calculated to be 1.65L from the 20g mixed virgin plastics if there were
no interaction among the plastics. However, the volume of the collected non-
condensable gases from the pyrolysis of mixed virgin and post-consumer plastics was
2.13L and 1.92L, respectively. The gas volume of both plastic mixtures is higher than
the expected gas volume, 1.65L. Therefore, the interaction promoted the gas production.
It was reported that the increased proportion of gas product could be taken as an
indicator for the interaction of various plastic. [21, 24, 108] However, the effect of
mixed plastic interaction in this study was not as significant as reported by Williams.
[21, 24] This is likely to be due to the higher PS composition in the post-consumer
149
plastic mixture in this study than that in Williams study. In high reflux rate pyrolysis,
the percentage of non-condensable gas from pyrolysis of individual plastics was 4% for
PS, 18.3% for LDPE and 15.7% for PP. (Table 6-8) As a result, higher PS content led to
a lower proportion of non-condensable gases in the mixture of PP, PE and PS.

There was a small quantity of char found at the bottom of the reactor in the pyrolysis of
mixed plastics. Most of the char was black carbon chips with metal shine. This char was
mainly generated from pyrolysis of PS as the char content from the PS pyrolysis was
much higher than other plastics. The char content in the post-consumer plastic product
was three times as much as that in the virgin plastic product, again likely due to the
higher PS content in the mixture and the paper contamination on the post-consumer
plastics.

Table 6-8 Product distribution from pyrolysis of individual virgin plastics, and pyrolysis of
mixed virgin plastics and mixed post-consumer plastics
Product distribution Gas Liquid Char
LDPE 18.3%* 81.7% -
PP 15.7%* 84.2% -
PS 4.0%* 93.0% 3.0%
Virgin mixture* 17.5%** 82.0% 0.5%
Post-consumer mixture** 7.2%** 92.3% 1.5%
* The value is calculated from molecular weight and the volume of collected gases.
** The value is calculated by the difference of material and the other two products.

150
6.3.4. Conclusions
The product from pyrolysis of the mixed PE, PP and PS is very complex. However,
most of the major components are also present in the products from pyrolysis of
individual plastics. The effect of the interaction among the plastics during the pyrolysis
on the distribution of liquid product is not significant. However, the interaction
promotes the production of non-condensable gases during the pyrolysis.

Styrene is the dominant component in the product, which is promoted by the interaction.
The char content in the plastic mixture is small, and is mainly determined by the content
of PS in the mixture. Contamination of paper labels on the post-consumer plastics may
result more char content in the product.

151
7. Study on Semi-scale Pyrolysis Plant
7.1. Introduction
Pyrolysis of waste plastic has been intensively investigated in recent years because of
the concerns for the solid waste disposal and the crisis of future energy. There are a
number of pyrolysis plants in the world to convert waste plastic to energy and liquid
fuels. [18] In Europe, 22% of the post-consumer plastics have been treated for energy
recovery. A Japanese pyrolysis plant was recently built in Niigata city with an official
annual capacity of 6000 tons and this process is shown in Figure 7-1. [89] Another
pyrolysis plant was recently constructed in Sapporo which has a capacity of 40 tons
municipal waste plastic per day. However, there is no commercial plant built in New
Zealand for the pyrolysis of waste plastic. [7]

Due to the lack of understanding of the pyrolysis conditions on the products, the
products are only used as boiler fuel or for power generator. In addition, there are some
issues and concerns in the waste plastic pyrolysis which limit the commercialisation of
the technology. In the municipal waste plastic stream, there is a certain amount of PVC
and PET. The major products from pyrolysis of PET and PVC contain benzoic acid and
hydrogen chloride which are not desirable in the transport fuels. Therefore, the current
pyrolysis plants for treating municipal waste plastic normally have to apply a
dechlorination and HCl removal treatment. [17-18]

In this part of research, the aims were to design and build a semi-scale continuous
pyrolyzer to experimentally investigate the pyrolysis products using virgin and post-
consumer PE. Previous investigation in this study has found that the three types of
plastics have similar cracking temperature and the pyrolysis products are mainly
hydrocarbon products. Therefore, the effect of semi-scale plant on the product of PE
pyrolysis was experimentally investigated in this part of study. The difference of batch
and continuous processes was also investigated. The actual energy consumption of the
process can be measured on this semi-scale plant.
152

Figure 7-1 Scheme of the Niigata pyrolysis plant [89]

Most of the current commercial pyrolysis plants are using continuous pyrolysis process
while plants applied for research purposes are normally laboratory scale, batch process
apparatuses. This part of the study will use the semi-scale continuous pyrolysis system
to develop optimal design and operation conditions thus to maximise desired diesel
range products. A typical continuous pyrolysis plant consists of three sections: feeding
system, pyrolysis section, and product separation, therefore, each part of the system will
be analysed and its design will be determined based on the follow analysis.
Pyrolysis reactions occur in oxygen free or inert environment. Therefore, the feeding
system has two major functions: prevent the air flowing into pyrolyzer and control the
feeding rate. In practical operation, the feeding system also needs to be able to prevent
pyrolysis vapour escaping from the reactor. A popular feeding system applied in the
continuous reaction is to pre-melt the plastic into liquid and send the melted plastic into
the reactor. The air is removed from the melted plastic by this way. Due to the poor heat
conductivity and the high viscosity, plastic can hardly be heated evenly. Some types of
plastic may start cracking before others melt because of the temperature gradient within
153
the melting chamber. Another popular system is to use inert gas to purge the air off
from the feedstock and feed the plastic into the reactor with an extruder. The advantage
of using an extruder is that the feeding rate can be precisely controlled.
In the pyrolysis section, reactor type is a key factor that determines the retention time,
product distribution and separation under given operation conditions. In the literature
review, fixed-bed, fluidized bed, and rotary kiln type of reactors have been reported.
[21-22, 24, 29, 44-46, 61, 69, 87-88, 111, 115, 128-129] Each type of the reactor has
different features and advantages.
Fixed bed reactor is relatively simple in design and construction, and normally used in
batch process. It can achieve very high conversion efficiency with proper control. The
quality of the oil product can be equivalent to the mixed conventional fuels. [61]
However, large temperature gradients exist in the reactor, which cause difficulties of
temperature control and scale-up problems. The heat transfer is not efficient for a fixed
bed reactor; therefore, it requires large surface of heat exchanger. The size of feedstock
particles should be very small and uniform in order to improve the heat transfer. Due to
the above features, fixed bed reactor is normally applied in research but not for large
commercial use. An example of the fixed bed reactor is shown in Figure 7-2. [24]

Figure 7-2 Scheme of a fixed bed apparatus [24]
154

Fluidized bed reactor has been commonly used in large scale pyrolysis plants as it can
provide very efficient heat transfer and much less temperature gradient than those of a
fixed bed reactor. The efficient heat transfer is due to the uniform turbulent mixing
between carrier gas and solid particles in the reactor. (Figure 7-3) [88] However, the use
of bed material and separation of the carrier gas may be disadvantageous which can
reduce the conversion efficiency and the quality of the products compared to the fixed
bed reactor Fluidized bed reactor is suitable for continuous operations which produces
pyrolysis product with consistent quality. The small temperature gradient and good
temperature control in the fluidised bed reactor allow it to be used in large scale
operations. Additional advantages of the fluidized bed reactor include flexibility of
using catalyst and varying retention time by changing the carrier gas velocity.

Figure 7-3 Scheme of a fluidized bed apparatus [88]

155
Rotary kiln reactor is another popular type for commercial applications. The rotary kiln
reactor is a horizontal cylinder in which the feed plastic is moved from one end to the
other by a screw. The heat is provided by the heating source in the cylinder shell jacket
through the wall to the moving plastics inside. The heat transfer in the rotary kiln
reactor is not as good as in the fluidised bed reactor thus long cylinder kiln is normally
required for long retention time. [61] There is a high longitudinal temperature gradient
along the length of the rotary kiln reactor. The cylinder kiln has different functions
along the process as shown in Figure 7-4 for pyrolysis of LDPE. [45, 60] In the figure,
the first section of the screw under the hopper of LDPE-oil mixture moves the feedstock
into the pyrolysis section. The temperature in the pyrolysis section is above the cracking
point of LDPE thus the LDPE is pyrolyzed in this section. The products are then
removed to the next section for product collection and separation. The rotary kiln
reactor has the primary pyrolysis reactions only so that there are less non-condensable
gases and more heavy hydrocarbons produced during the process with regard to
conventional fixed-bed reactors. [29-30] This type of reactor is relatively easy to
operate for plastic feeding and product removal. Particularly, the char generated from
the plastics can be removed from the pyrolysis section.

Figure 7-4 Scheme of a rotary kiln apparatus [45, 60]

156
7.2. Design and construction of the continuous waste plastic
pyrolysis system
In this part of the study, a continuous pyrolysis apparatus was designed and built for
investigating and optimisation of the waste plastic pyrolysis process in a large scale
reactor. The apparatus was designed for pyrolysis of PE, PP, and PS and their mixture.
The differences between virgin and post-consumer plastics in the continuous process
were investigated as well. The products were separated by its boiling points and
collected as wax, diesel, petrol, and non-condensable gases. The continuous process can
then be controlled by altering operation conditions and system configuration to achieve
the optimized product distribution. As one of the major objectives for this study was to
maximize the diesel range product, the process will be optimized towards high diesel
range distribution. The diesel range product produced from normal pyrolysis systems
cannot meet New Zealand diesel regulation requirements as outlined in Table 7-1. [130]
However, it was hoped that the products from this continuous process apparatus
designed in this study would be able to meet these regulation requirements. The diesel
derived from plastic has some advantages compared with the retailed diesel derived
from cruel oil.
Table 7-1 New Zealand requirements for diesel regulation [130]
Property Limits Test method
Fatty acid methyl esters
(% volume)
5 maximum EN 14078
Density at 15C (kg/m
3
)
820 minimum
850 maximum
ASTM D1298
Distillation95%
volume recovered at (C)
(T95)
360 maximum ASTM D86
Cetane
51 minimum cetane index, or 51
minimum cetane number and 47
minimum cetane index
Cetane number:
ASTM D613 or
ASTM D6890
Cetane index: ASTM
D976
Water content (mg/kg) 200 maximum IP 438
157
Property Limits Test method
Total contamination
(mg/kg)
24 maximum IP 440
Colour (ASTM colour) 3.0 maximum ASTM D1500
Cloud point (C) and cold
filter plugging point (C)
Summer maxima: Auckland and
Northland: +6 cloud point; rest of
New Zealand: +4 cloud point.
Winter maxima: +2 cloud point
and 6 cold filter plugging point
Cloud point: ASTM
D5773 cold filter
plugging point: IP 309
Sulphur(mg/kg)
50 maximum
10 maximum on and from 1
January 2009
IP 497 or ASTM
D5453
Polycyclic aromatic
hydrocarbons (% mass)
11 maximum IP 391
Filter blocking tendency
2.5 maximum; fuel must be of
acceptable filterability so that it is
fit for common purposes
IP 387 or ASTM
D2068
LubricityHFRR wear
scar diameter at 60C
(m)
460 maximum IP 450
Viscosity at 40C mm
2

per second
2.0 minimum
4.5 maximum
ASTM D445
Oxidation stability (g/m3) 25 maximum ASTM D2274
Carbon residue (on 10%
distillation residue) (%
mass)
0.2 maximum ASTM D4530
Copper strip corrosion (3
hours at 50C)
Class 1 maximum ASTM D130
Ash (% mass) 0.01 maximum ASTM D482
Flash point (C) 61 minimum ASTM D93
Table 7-1 New Zealand requirements for diesel regulation (Continued)
158
7.2.1. Determination of apparatus functional sections
The continuous process requires a system that can feed the material continuously. In
order to control the feeding rate, an auger with a rotation speed controller was applied to
feed the plastic particles into the pyrolyzer. Another requirement of the feeding system
is to prevent the air contamination into the reactor or to prevent the pyrolysis vapour
leaking from the reactor into the ambient atmosphere. An auger with sufficient length
and relatively small feedstock dimensions can prevent the pyrolysis vapour leaking
from the reactor. (Figure 7-6, Figure 7-8)

The batch reactor that used previously was a relatively slow pyrolysis process based on
the heating rate and the cracking temperature achieved. The power input in the batch
reactor was not sufficient to pyrolyze the plastic and to vaporize the products in a few
seconds. Therefore, the temperature remained at the plastic pyrolysis point for several
minutes during the pyrolysis. In this part of the study, a fixed-bed reactor was selected
based on scale of the system and the results from the previous experiment using the
batch reactor. Based on the previous experiments, char accumulated at the surface
where the reactions occurred. Therefore if this occurs in the fixed bed reactor, the char
can not be removed easily. The present of char affects the heat exchange and limits the
maximum process running time. The maximum capacity of the slow pyrolysis plant was
also limited by the input power and the feeding rate. In normal operation in the
continuous fixed bed pyrolysis reactor, the energy transferred to the plastics is equal to
the energy requirement for the pyrolysis and the vaporization. In the mean time, the
mass of the plastic fed in is the same as that of the plastic vaporized; therefore, the
liquid level should remain constant in the reactor. The temperature of the melted
plastics also remains constant close to the cracking temperature.

From the previous experiments of batch pyrolysis of the plastic, the liquid is a mixture
of hydrocarbons with various molecular weights. This mixture needs to be separated
through distillation into different fractions in order to obtain liquid products which
match the current retail liquid fuels. The function of the separation section on the
apparatus is to separate hydrocarbons into different ranges which correspond to retails
159
products such as diesel, petrol, wax and LPG. According to the boiling points of the
products obtained from previous experiments, the products can be separated into four
groups: hydrocarbons heavier than diesel (wax), hydrocarbons in the range of diesel,
hydrocarbons lighter than the diesel; and non-condensable gases (LPG). Conventional
diesel is a mixture of hydrocarbons from C
10
to C
25
with a normal distribution as shown
in Figure 7-5 in which the liquid products from previous batch pyrolysis of LDPE are
also illustrated. To separate the LDPE pyrolysis products, two re-boilers (Pot 1 and Pot
2) are designed to control the boiling points of the liquid products. Two corresponding
distillation columns are also designed, each being mounted above the corresponding
reboiler to control the desired fractions of the liquids.

Figure 7-5 GC results of diesel (top) and PE condensable products (bottom)

The designed continuous pyrolysis apparatus is shown in Figure 7-7. Figure 7-7 is for
the actual system and Figure 7-8 is for the flow sheet diagram. This system can produce
four groups of products: wax, high quality diesel, petrol range product, and non-
condensable hydrocarbon gases. The pyrolysis system also includes safety guard
devices to prevent potential hazards, failure of electrical parts, or other accidental
leaking and breakage.

160

Figure 7-6 Engineering scheme of the apparatus

Figure 7-7 Photo of the apparatus
161

Figure 7-8 Scheme of continuous pyrolysis apparatus
162
7.2.2. Design calculations of the pyrolysis apparatus
According to the energy balance calculation described in Section 3.2.2, the theoretical
energy demand for pyrolysis of 1 kg PE is 1048 kJ to generate a product of10% w/w
C
3
H
6
, 30% C
8
H
16
, 40% C
16
H
32
and 20% C
28
H
56
. The further calculations for energy
demand feeding rate in the designed system are based on this product distribution.
However, in practical pyrolysis, other factors affecting the energy requirements
should be considered for the design which include heat loss, reflux rate and retention
time.

The feeding rate of the waste plastic (kg/min) to the pyrolysis system is mainly
determined by the performance of the pyrolysis reactor section. Therefore, the
calculations of energy demand and feeding rate begin with the pyrolyzer. There is a
total 10 kW energy supply to the pyrolyzer, 6 kW element installed on the bottom
(inside) of the pyrolyzer and a 4 kW element installed on the pyrolyzer wall. (Figure
7-9) The total 10 kW power supply is equivalent to 36MJ energy input in one hour.
This amount of energy can theoretically convert 34.4 kg/h PE into pyrolysis products
based on the theoretical energy requirement, 1048 kJ/kg. Assuming that 30% of the
energy is lost during the pyrolysis process, the estimated maximum capacity of the
pyrolyzer is then estimated to be 24 kg/h PE into the hydrocarbons with the
distribution given early.

The designed pyrolyzer system is operated in slow pyrolysis. The element on the
reactor wall is folded within 100 mm from the reactor bottom and the power output is
adjusted by the level of the melted plastics in the reactor. The maximum capacity can
only be achieved when the internal element is completely immersed in the melted
plastics, which means that level of the melt plastics is higher than 100 mm from the
bottom. When the pyrolyzer is operated with the level of the melted plastic less than
the 100 mm mark, the power to the elements is turned off thus the level of the melted
plastic will increase. Alternatively, when the melt plastic level in the reactor is 100
mm or higher, both of the internal and the external elements are turned on, thus
163
providing a higher pyrolysis production. When the feeding rate is lower than the
maximum capacity of the reactor, the power will automatically turned off till the
temperature drops below the pre-set cracking temperature by the feedstock or heat
loss. The feedstock was heated from under cracking temperature to the cracking
temperature until all feedstock was completely cracked and vaporized. Therefore,
there is not significant effect of the batch and the continuous processes on the
cracking reactions because both feedstocks were cracked as slow process. The only
difference is that the feeding and the cracking are continuous in the continuous
process while the feedstock is fed as a batch before the cracking in the batch process.

The pyrolyzer is shown in Figure 7-8. The main part of the pyrolyzer is a chamber
with dimensions of 100 mm (width) x 400 mm (length) x 200 mm (height). The wall
of the chamber is made of stainless steel. On the two 100 mm x 200 mm sides, two
pieces of glass are installed as windows that can continuously work under 720 C.

Figure 7-9 Photo of pyrolyzer

164
As shown in Figures 7-7 and 7-8, there are a series of separation devices following
the pyrolyzer which can separate the pyrolysis products into wax, diesel, petrol and
non-condensable gases, by controlling the boiling temperatures. These can be
achieved by a temperature controlled connection pipe, two distillation columns with
reboilers followed by a condenser. The connection pipe and the first reboiler (Pot 1)
are used to condense and collect the wax from the products. After this, the
hydrocarbons in the diesel range are separated in the first distillation column (Column
1) and are collected from the second reboiler (Pot 2). Then the hydrocarbons lighter
than the diesel range (petrol) are separated in the second distillation column and
condensed in the downstream cooler. Once the petrol range hydrocarbons are
condensed, they are collected in the petrol tank installed beneath the cooler. After the
cooler, the remaining non-condensable gases flow out of the system and flared off
with the Bunsen burner.

The separation of the diesel range product requires the adjustment of the highest and
lowest boiling points, and the level of separation. To achieve the boiling temperature
required, the power input into the two reboilers can be adjusted based on the required
boiling points of the liquid products to be collected. Two packing columns are
designed to control the level of the hydrocarbon separation. The dimensions including
height and the packing materials of the columns can be changed based on the
separation requirements. The actual maximum production rate must not exceed the
theoretical capacity of the pyrolyzer because other factors like heat loss will
significantly reduce the actual maximum capacity of the production. Therefore, the
theoretical maximum production rate, 34.4 kg/hr (9.56 g/s), was accepted for the
calculation of the dimensions of the separation pipeline. According to the maximum
production rate, the maximum volume of the product and the volume at different
temperature can be calculated. (Table 7-2)

165
Table 7-2 Expected value of products
Product
Expected
proportion
mass flow
(g/s)
MW
(g/mol) mol
Expected volume
flow at 400C
(L/s)
C3H6 10% 0.96 30 0.0319 1.76
C8H16 30% 2.87 112 0.0256 1.41
C16H32 40% 3.82 224 0.0171 0.94
C28H56 20% 1.91 392 0.0049 0.27
Total 100% 9.56 189.5 0.0794 4.38

The pipe connecting the pyrolyzer and the first reboiler (Pot 1) is 316L stainless steel
pipe with 48.4 mm inner diameter and 1.2 mm wall thickness. The cross section area
of the pipe is 0.002 m
2
which allows a maximum vapour velocity of the product at 2.3
m/s. Because some products are condensed in the pipe, the linear velocity of the
vapour in the following devices will gradually be decrease and will be less than 2.3
m/s. The temperature of the non-condensable gases is designed to be at about 30 C
with a volumetric flow rate of approximately 0.73 L/s. The non-condensable gases are
flared off by using Bunsen burner with a LPG ignition source. The pipe from the
separation section to the Bunsen burner non-condensable gases is 20 mm inner
diameter PVC pipe which allows a maximum gas linear velocity of 2.3 m/s with
pressure drop less than 45 Pa in total.

In the designed of system, the two re-boilers have the same shape and the same
dimensions, each consisting of a cone-shape section and a cylinder section above the
cone. (Figure 7-10) In the cone section, a set of 1 kW elements are installed on the
outside wall for heating. The temperature of the liquid inside each reboiler is
measured with two pairs of thermocouples. One pair of thermocouples is used for
temperature recording and the other pair for temperature control. The cylinder above
166
the cone is made of QVF glass that makes the visual observation possible. (Figure
7-11)

Figure 7-10 Scheme and dimensions of Pot 1

Figure 7-11 Pot 2 of the pyrolysis plant

167
As discussed previously, there are two packing distillation columns in the system for
separation of the hydrocarbons. Column 1 is made of 1.5 mm thick, 316L stainless
steel pipe with 50.4 mm outer diameter. The packing are copper rings with 5 mm
high, 5 mm in diameter, and 1 mm wall thickness. The copper rings were piled for
400 mm high in the column. Column 2 is a standard QVF glass pipe, which is 500
mm long and 51 mm in inner diameter. The packings in the Column 2 are 1 mm thick,
7 mm x 7 mm glass rings.

This pyrolysis system is monitored and controlled by a Shimaden SR92 digital
controller. (Figure 7-12) The temperatures in 20 locations are monitored or controlled
in the system and these locations are illustrated in Figure 7-8. In the 20 pairs of
thermocouples used, 8 are used for temperature control and 12 for temperature
recording.

Figure 7-12 Control panel of the apparatus

In the commissioning tests, significant reflux occurred in the feeding pipeline
between the feeding hopper and the pyrolyzer. Reflux was also found in the U shape
168
connection pipe between the pyrolyzer and the Pot 1. Therefore, the maximum actual
productivity achieved, 27.11kg/hr was less than the maximum theoretical production
rate 34.4kg/hr because of significant heat loss and reflux in the pyrolysis system.

7.3. Experimental
In the experiments, both virgin PE and post-consumer PE were tested on this semi-
scale continuous plant. The products were then compared with each other to find out
the effect of use, recycling and contamination. The virgin PE was 3 mm long and 3
mm wide white ovals. Its properties were described in Section 5.1.1 and Table 5-1.
Virgin plastic was tested on the continuous plant for comparison with the batch
process experiments. The whole system was purged with nitrogen gas for two
minutes. During the purging time, nitrogen gas was fed from the feeing port but the
plastic feeding valve, V
1
, as well as the exits of Pot 1 and Pot 2 were all closed. In this
way, the remaining air in the system was pushed out of the system from the outlet of
the non-condensable gas. After that, the internal element was set and hold at 550 C;
and the external element was set and hold at 500 C, at which the actual reaction
surface temperature was tested just over the PE cracking temperature. Once the
temperature of the reactor was hold steady, 1kg virgin plastic was fed into the reactor
with feeding rate at 1kg/hr. The power on Pot 1 and Pot 2 was turned of for a
complete separation of liquid and gaseous products. The one kg virgin plastic was
evenly fed into the reactor in one hour, then, V
1
was closed. The power of the reactor
was switched off at 10 minutes after V
1
was closed. At the time, no more products
were produced from the reactor. No flame came out of the Bunsen burner. After the
experiment, the liquid product was analyzed through GC with the same method as
used in Section 5.

The post-consumer PE used in the experiments was in the form of small chips
provided by a local waste recycling company near Christchurch, New Zealand. In the
recycling process, the waste plastics were crashed to 15 x 10 x 2 mm chips as shown
in Figure 7-13. However, some of the chips are too large to feed through the auger.
169

Figure 7-13 Pre-treated post-consumer PE used in the experiment.

Due to the feeding problems, the system was run as batch and in each run, 2.5kg of
post-consumer plastics were fed into the pyrolyzer at the beginning. Then, the
continuous plant was purged with nitrogen gas for two minutes. After the purging
process was completed, the reactor was heated up to 420 C. At this point, it is
assumed that the pyrolysis was about to start based on the previous lab scale test
results. Then the reactor was held at 420 C for 15 minutes to ensure the temperature
was uniform within the reactor and the plastics were melted. After this, the heating
elements both on the wall and at the reactor bottom were turned on at full capacity
and the target temperature was set at 550 C in order to generate fast pyrolysis
conditions. The start of the pyrolysis process was indicated by the temperature in the
U-shape connection pipe between the pyrolyzer and Pot 1. During the pyrolysis, part
of the vapour generated from the pyrolyzer started to condense first in the U-shape
connection pipe and collected in Pot 1. Then the remaining vapour flew further into
Column 1 from which some fraction of the vapour was condensed and flew back to
Pot 1 and the rest moved further to the downstream cooler. The condensed liquid from
this cooler and from Column 2 was collected in Pot 2 which the non-condensable
gases exited from the outlet of the system and flared off.

After about 6 minutes, the temperature in the U-shape connection pipe between the
pyrolyzer and Pot 1, T
6
, started decreasing indicating that the end of primary cracking
170
was completed. The power was then switched off when the temperature in the U pipe
dropped for ten minutes. After the experiment, the liquid products in Pot 1 and Pot 2
were collected and mixed together in an 80C water bath for GC analysis.

Condensed product analysis
The condensed product from pyrolysis of the virgin plastic was analysed with GC.
(Figure 7-14) The hydrocarbons detected in both of the products are mainly straight
chain hydrocarbons ranging from C
5
to C
42.
The peaks of the straight chain
hydrocarbons with the same carbon chain number were grouped together on the GC
graphs. As defined in Chapter 5, the three dominant peaks in each group are , -
dialkene, 1-alkene, and n-alkane from left to right in the GC graphs.
171
(a)
(b)
(c)
(d)
Resistance time (minute)
Figure 7-14 GC graphs of analysis results
Note:
172
Virgin PE pyrolysis product, low reflux rate, batch process, lab-scale reactor (a)
Post-consumer PE pyrolysis product, batch process, semi-scale reactor (b)
Virgin PE pyrolysis product, continuous process, semi-scale reactor (c)
Virgin PE pyrolysis product, high reflux rate, batch process, lab-scale reactor (d)

By examining the GC graphs, it is apparent that the concentration of the light
hydrocarbons appearing in the first five minutes on the GC graphs is lower in (a) and
(b) than in (c) and (d). This is due to the volatiles loss in the hot water bath process.
There are 10% w/w and 13% w/w loss in (a) and (b); respectively. (c) and (d) were
analyzed straight after collection in order to prevent any product loss. It can be
observed that the product from continuous process, (c), has a very similar distribution
as that of product from high reflux rate batch process, (b), except for the high
proportion of the heavy hydrocarbons which came out after 25 minutes from the
beginning. The reduction of heavy hydrocarbons in the high reflux rate process
products has been identified as the effect of the secondary cracking reactions. Hence,
the product from the continuous process is more like the low reflux rate product, (a),
rather than the high reflux rate product. It can also be found in Figure 7-14. The
difference in the light hydrocarbons is due to the hot water bath process. (b) has also
got similar distribution as (a). However, the proportion of C
12
to C
16
is lower in (b)
than that in (a).

The distribution of the product from the semi-scale and the lab-scale plants has been
compared in Table 7-3. From the pyrolysis of virgin PE, 89.03% w/w of the total
feedstock was condensed and less than 0.1% solid mixture of char and small quantity
of wax was found being left in the reactor. The rest of the feedstock, 10.87 % w/w, is
believed to be the non-condensable gases. (Table 7-3) The proportion of char in both
continuous and batch processes with the semi-scale plant was insignificant, which
was similar to the batch pyrolysis of the PE. However, the char content in post-
consumer PE pyrolysis is higher than that in virgin PE pyrolysis.
173

Table 7-3 Comparison of product distribution of different plants
PE product Gas* Condensed
product
Char Total
Semi-scale
plant
Virgin 10.87% 89.03% <0.1% 100%
Post-consumer 11.56% 88.24% <0.2% 100%
Lab-scale
plant
Low reflux rate 6.9% 93.1% - 100%
Medium reflux
rate
16.7% 83.3% - 100%
High reflux rate 18.3% 81.7% - 100%
*The weight of gas product is a calculated value from the total feedstock and the
collected product.

According to the proportion of the gaseous product, the product from continuous
process was equivalent to the product from the lab-scale plant with a reflux rate
between low and medium reflux rate. (Table 7-3) However, there is no reflux effect in
the semi-scale plant because of the design. The semi-scale plant should perform like a
low or no reflux rate process. By comparing the distribution of the condensed
products, it was found that the distribution of product from semi-scale plant is very
close to that from lab-scale plant. (Table 7-4) The proportion of heavy molecular
weight hydrocarbons, wax, in the semi-scale plant product is even more than in the
lab-scale plant product. This high proportion of heavy hydrocarbons indicates that no
reflux effect in the semi-scale plant, which match the design of the plant and
performed with no reflux process. Therefore, the non-condensable gases are totally
from the primary cracking in the semi-scale plant. However, there is significant
difference in the proportion of the non-condensable gasses between the two reactors,
11.56% for semi-scale reactor and 6.9% for lab-scale reactor operating at low reflux
rate. This is caused by the different cracking temperature. By comparing with the
174
temperature at cracking surface, it was found that the reaction surface temperature in
semi-scale reactor (500C) is about 50 C higher than that in lab-scale reactor (450C).
According to other references, higher reaction temperature leads to higher gas
proportion in the products. [42], [44]

Table 7-4 hydrocarbon distribution in the condensed product
Product
Petrol
C
5
-C
12
Diesel
C
13
C
20
Wax
C
21+
Total
Virgin continuous semi-
scale (c) 33.42% 30.32% 36.26%
100%
Post-consumer, batch
semi-scale (b)* 33.22% 29.83% 36.95%
100%
Virgin high reflux rate
lab-scale (d) 36.16% 51.35% 12.49%
100%
Virgin low reflux rate
lab-scale (a)* 34.07% 30.85% 35.08%
100%
Note:
* The compensation has been added for the petrol loss.
(a), (b), (c), (d) refer to Figure 7-14.

Based on the GC analysis, although the hydrocarbons with carbon chain number from
5 to 12 accounts for 33.42% in the virgin PE pyrolysis product, which is much higher
than that of post-consumer PE pyrolysis (23.24%) due to the volatile loss as
mentioned before. The difference of the proportion of the other two groups would be
less than 1% when the volatile loss in the post-consumer PE pyrolysis product is
compensated to the petrol range product in Table 7-4. Therefore, the distribution of
175
the product from post-consumer PE pyrolysis is virtually the same as that in the
product of virgin PE pyrolysis.

The components in products from both plants are almost the same although the
concentration may vary within a relatively small range. (Figure 7-14) There were 196
and 204 peaks found, respectively, in the products of post-consumer PE and virgin
PE. Heavier molecular weight components are found compared to that in the product
from the high reflux rate lab-scale process. (Section 5.1.4) As the concentration of
each peak is the area covered by the peak thus it is proportional to both the width and
the height of the peak. 1-alkenes and n-alkanes are the most important peaks in all
groups of both virgin and post-consumer PE products. However, the concentration of
1-alkenes is lower in the post-consumer PE product than in the virgin PE product.
Similarly, the concentration of , -dialkenes is also lower in the post-consumer PE
products than in the virgin PE product. This could be caused by the difference of the
feedstock. The contamination on the post-consumer PE is mainly paper tags attached
on the plastic chips, which are mainly cellulose and hemicelluloses. Hydrogen is a
main product from cracking of wood or paper. [131-132] Under the pyrolysis
conditions, there could be hydrogenation reactions in the processes. [2, 38, 93] The
hydrogen produced from cracking of the contaminants could saturate the double bond
and formed more n-alkanes in the final products. As the products in both the post-
consumer PE pyrolysis and the virgin PE pyrolysis were from the primary cracking
because they were immediately removed after produced. Therefore, heavy
hydrocarbons, up to C
42,
and unsaturated hydrocarbons are rich in the products.

Pyrolysis process analysis
In the continuous process, the power of each element on the plant is self-controlled by
the digital program controller. However, the temperature was strongly related to the
power on/off status rather than the reactions in the plant. Therefore, the temperature
profile of the continuous process can not provide much information about the
pyrolysis process. However, the temperature profiles of the batch process contained
useful information because the power was not switch on and off that often. The
176
temperature profiles of the system in the pyrolysis of post-consumer PE are shown in
Figure 7-15. From the temperature profiles, the process had three stages: plastic
melting, cracking, and cooling. T
4
is the temperature at inner surface of the reactor,
which shows the reaction temperature. In the first five minutes, the reactor was heated
up and held at 420 C. There was no product coming out during this period until the
internal and the external elements were switched on to the new set point of 550 C.
Product started being produced once the element temperature started increasing again
at 20 minutes from the beginning. The hot product flow affected the temperature of
other thermal indicators. The temperature inside the U-shape connection pipe (T
6
) and
the temperature at the entrance of Column 1, T
17,
show the product flowing into Pot 1
and Pot 2, respectively. No product was coming out of the pyrolyzer during the
melting stage, hence, T
6
and T
17
also remained at the room temperature. This cracking
process is very similar to the low reflux rate lab-scale batch process that was
described in the previous chapters.

0
100
200
300
400
500
600
0 500 1000 1500 2000
Reacti on ti me (Second)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
T6
T15
T17
T4
T18

Figure 7-15 Temperature profiles of the continuous pyrolysis process

177
The cracking process occurred between 1200
th
second and the 1585
th
second in which
period the temperature inside the reactor (T
4
) increased to 500 C and then remained
relatively constant at that temperature. During this period, T
6
increased rapidly to 450
C and then remained at that temperature very briefly before it decreased. This
indicates massive products produced and flew out at 450 C during this period. The
U-shape pipe was insulated with glass fibre rope to reduce heat loss and reflux of the
condensate to the reactor. During the cracking period, it was observed that some
liquid hydrocarbons were condensed and collected in Pot1, but a larger amount of
liquid hydrocarbons was collected in Pot2. The flame of the non-condensable gases
above the Bunsen burner was orange and was about one meter high.

The sudden increase of T
17
was noticed at the 1450
th
second, which shows the
remaining vapour flowing from the Column 1 into Condenser 1. However, in the
experiment of the PE pyrolysis, all of the liquids were collected only in Pot 1 and Pot
2 while no liquid was found in the petro tank which was caused by the lower
temperature of the vapour from Condenser 2 even the cooling water was turned off to
the Condenser 2. The temperatures after the Condenser 2 (T
18
) and above the petrol
tank (T
15
) remained at room temperature throughout the experiment.

Towards the end of the pyrolysis at the 1585th second from the start, the temperature
in the pyrolyzer (T
4
) started increasing rapidly whereas the temperatures in the U-
shape pipe (T
6
) and above Column 1 (T
17
) started decreasing. These indicate the end
of the cracking stage and the start of the system cooling. The increase of T
4
was due
to less energy requirement after the plastics had been pyrolyzed. As a consequence,
no vapour was generated thus there was no vapour flow in the system and the
temperature in the system dropped. After 30minutes, the experiment was completed
and the power to the heating elements was switched off. Then the system was cooled
down to the room temperature.

178
After the system was cooled down to room temperature, the liquid products collected
in both Pot 1 and Pot 2 were taken out. In the pyrolysis of post-consumer PE, the
condensed product from Pot1 was yellow wax at 20 C but it was melted into liquid
when being heated to about 80 C. The product from Pot 2 was clear yellow liquid at
20 C. The two products were melted and mixed in a flask and analyzed through the
GC used previously in Section 5. (Figure 7-16) The flask was put in a water bath at
80C for one hour to homogenize the product. However, some of the volatile
hydrocarbons were vaporized due to heating in the hot water bath.

The products from virgin PE pyrolysis were only melted for GC analysis but were not
heated in the hot water bath. Therefore, there was less volatile product loss in the
liquid product obtained from the pyrolysis of virgin PE compared to that of pyrolysis
of post-consumer PE.

Figure 7-16 Collected liquid product from pyrolysis of post-consumer PE.

Energy consumption
The energy required for pyrolysis of 2.5kg post-consumer PE can be calculated from
the input power and the elapsed time. The total power input from the heating elements
in the pyrolyzer is 10kw when these elements are switched on at full capacity.
However, the elements were switched off twice during the cracking stage to control
the temperature; from the 1430
th
to the 1440
th
second, and from the 1519
th
to the
1562
nd
second. The total time of the cracking stage was from the 1200
th
to the 1585
th

179
second except the time when the power of the elements was off. Thus, 2.5 kg PE
waste requires heating from 10kw elements for 332 seconds to complete the primary
cracking and vaporization, which is 3.32 MJ. Therefore, the actual maximum
production rate is 27.11 kg/hr when the feedstock is pre-heated to the cracking
temperature. Therefore, the energy consumed for the pyrolysis and the vaporization is
1.328 MJ/kg. Based on the pyrolysis reactions, the theoretical energy requirement for
pyrolysis of the post-consumer PE is 1.033 MJ/kg based on the discussion in Chapter
3. Table 7-5 gives the detailed energy demand for production of each hydrocarbon
group in which C
3
H
6,
1-C
8
H
16,
1-C
16
H
32,
1-C
28
H
56
, respectively, represent C
1
to C
4
, C
5
-
C
12,
C
13
C
22,
and C
23+
.

Table 7-5 Theoretical energy consumption of PE pyrolysis
1kg PE C
3
H
6
1-C
8
H
16
1-C
16
H
32
1-C
28
H
56
Total
w/w 11.56% 29.49% 32.90% 25.84% 100%
mol 2.75 2.63 1.47 0.66 7.51
Hr kJ/mol 23.00 23.00 23.00 23.00 172.81
H kJ/mol 24.12 72.32 163.34 304.12 697.19
Hv kJ/mol 33.76 50.42 162.95
Total Energy kJ 129.69 339.87 347.74 215.63 1032.94
Where: Hr is the energy required for the cracking reaction. H is the energy required
for heating the compound. Hv is the heat of vaporization for the hydrocarbons. The
assumption of the calculation is under 1 atm. The pyrolysis products were at 400 C.

180
7.3.2. Conclusions
According to the experiment with the semi-scale apparatus, negligible difference was
found between continuous pyrolysis process of virgin PE and batch pyrolysis process
of post-consumer PE. The process of the pyrolysis on the semi-scale plant is very
similar to the low reflux rate process on the lab-scale plant.

In the pyrolysis of PE with the semi-scale plant, the distribution of the condensed
product is almost the same as that of low reflux rate process with the lab-scale plant.
10.87% w/w and 11.56% w/w of the virgin and the post-consumer PE were converted
to non-condensable gases. Because of no secondary cracking reactions in the process,
the non-condensable gases were produced during the primary cracking reaction. The
proportion of the gaseous product is higher from the semi-scale plant than from the
lab-scale plant because the semi-scale plant has higher reaction surface temperature.
In both cases, negligible amount of char was found in both virgin and the post-
consumer plastic products. The components in both products are also very similar. 1-
alkenes, n-alkanes, and , -dialkenes are the dominant hydrocarbons in the products.
The proportion of dialkene in the virgin PE pyrolysis product is significantly higher
than that in post-consumer PE product from the semi-scale plant. The proportion of n-
alkane is higher in post-consumer PE product than that in virgin PE product. These
could be affected by the contamination in the post-consumer PE.
The experimental energy consumption was measured as 1.328 MJ/kg.
181
8. Conclusions and future work
8.1. Conclusions
In this PhD study, pyrolysis of the hydrocarbon polymers, PE, PP and PS was
investigated both theoretically and experimentally in a lab-scale reactor for
maximizing the diesel oil products. Factors which affect the pyrolysis process have
been identified and quantified from the investigation. Based on the achievements, the
distribution of the product and the process was optimized. A semi-scale plant was
built based on the results of studies on the lab-scale reactor.

From the experiments on the PE pyrolysis, three types of products can be produced
which include non-condensable gases, condensed liquid hydrocarbons and char. The
distribution of the product varies greatly under different reaction conditions. For
example, char content was 13%w/w under certain conditions but can be minimized to
less than 0.2%w/w with the semi-scale plant. The proportion of non-condensable
gases is 18.3% w/w from the experiment in pyrolysis of PE with high reflux rate as
described in Chapter 4, but this is reduced to only 6.9% w/w in PE pyrolysis with low
reflux rate as presented in Chapter 5. Non-condensable gases are generated from
random cracking reactions. Higher reaction temperature or heating rate favours higher
production of non-condensable gases. According to GC and Micro-GC analysis, the
straight chain hydrocarbons are dominant in the non-condensable gases, liquid and
wax. They are mainly 1-alkenes, n-alkanes, and , -dialkenes with carbon number
ranging from 1 to 45+.

It was found that heavy molecular weight hydrocarbons produced from primary
cracking can be further cracked into light molecular weight products through a
secondary cracking process. This secondary cracking process has significantly
influence on the distribution of the product. This process converts heavy
hydrocarbons into gas or light liquid product. At high reflux rate, 1-alkenes and , -
dialkenes are significantly reduced. This secondary process can be controlled by
182
adjusting the reflux rate of the primary product. This find is new in this field as other
researches only alter the factors which only affect the primary cracking, such as
temperature, pressure, catalyst, or resistance time. With the adjusting of the reflux rate
in the pyrolysis, the quality of the product can be optimised which can be very useful
for commercial plant to achieve target products.

The proportion of char was negligible in all experiments both with the lab-scale
pyrolysis reactor and with the semi-scale pyrolysis reactor. Carbon is the dominant
element in the char in the SEM-EDS analysis results.

Some zeolite catalysts were tested to reduce the heavy molecular weight wax. It was
found that the catalyst of NKC-5 (ZSM-5) is the most effective catalyst among other
zeolites tested.

Pyrolysis of PP was also investigated in this study. It is found that the secondary
cracking also has effects on the pyrolysis product but the effect is not as significant as
that on PE. The high reflux rate PP pyrolysis product consists of 15.7% non-
condensable gases, 84.2% condensed liquid product, and less than 0.25% char. The
conversion rate to fuel is over 99.7% which is the higher than any reported values in
literature. In the PP pyrolysis, the methyl side group in PP structure breaks off
through chain strip cracking reactions, therefore, the methyl-radicals are combined
with other free radicals, forming propene or other oligomers. Propene is the dominant
component in the gases, which accounts for 44% v/v. In the liquid product of PP
pyrolysis, 1, 3, 5 - trimethyl - cyclohexane (C
9
H
18
) is identified to be one of the
dominant components, which accounts for 21% w/w. The low molecular weight
oligomers with 2 to 5 propene units accounts for 68% of the total liquid product.

The pyrolysis process of PS is different from those of PE and PP. In the pyrolysis,
most PS molecules are cracked into small molecular weight hydrocarbons in the
183
primary cracking through chain strip reactions. In the PS pyrolysis products, there are
4% non-condensable gases, 93% liquid, and 3% char. The proportion of PS pyrolysis
gases is much less than that of PE and PP. In the PS pyrolysis gas product, there is
19% v/v hydrogen which is not found in PE pyrolysis gas product. In the PS pyrolysis
liquid product, 92% (w/w) is found to be five aromatic compounds and styrene is the
dominant component that accounts for 68.59%, which has further confirmed the chain
strip reactions in the PS pyrolysis process. The char from the PS pyrolysis is mainly
pure carbon that is similar to the char from pyrolysis of PP and PE. However, the
proportion of the char in the PS pyrolysis is much higher than that in the pyrolysis of
PP and PE.

By comparison of the pyrolysis of individual HDPE, LDPE, PP, and PS, it is found
that HDPE, LDPE, and PP have very similar cracking temperature, 450C. However,
PS has a relatively low cracking temperature, 320C. Therefore, the plastic mixture of
these plastics starts cracking below 450C due to the interactive effect of PS. The
interaction among the plastics promotes the production of non-condensable gases
during the pyrolysis. However, the effect of the interaction on the distribution of
liquid product is not significant. Contamination of paper labels on the post-consumer
plastics may result in higher char content in the product but no significant effect on
the liquid and gaseous products has been found in this study.

In this study, a semi-scale continuous pyrolysis plant was built in Department of
Chemical and Process Engineering, with the maximum capacity of 27.11 kg PE /hr. In
the PE pyrolysis experiments on the semi-scale plant, the plastic feedstock only
undergoes the primary cracking, and the pyrolysis product is removed and separated
through the following separation distillation columns. It is found that the liquid
products have a similar distribution as those of PE pyrolysis at the lab-scale reactor
with low reflux rate. The pyrolysis process in the semi-scale plant is also similar to
that in the lab-scale plant. The major components in the PE pyrolysis product from the
semi-scale pyrolysis include hydrocarbons of 1-alkenes, n-alkanes, and , -dialkenes
which are the same as those from the PE pyrolysis at the lab-scale reactor. However,
184
the proportion of non-condensable gases from semi-scale plant is much higher than
that from PE pyrolysis at the lab-scale reactor with low reflux rate. This is due to the
high reaction temperature during the pyrolysis process in the semi-scale plant. Further
analysis of the pyrolysis products has found that there is lower proportion of
unsaturated hydrocarbons in the post-consumer PE than in the virgin PE. This is
possibly due to the contamination in the post-consumer PE.

The energy consumption was calculated based on pyrolysis kinetic models.
Theoretically, it requires 1.033 MJ to pyrolyze 1kg PE into hydrocarbons with a
certain distribution. The calorific value of the hydrocarbon products is about 42.3
MJ/kg. The energy consumption for the pyrolysis and vaporization of PE was
measured as 1.328 MJ/kg on the semi-scale plant experiment, which is les than 3% of
the energy possessed by the pyrolysis products. Therefore, the plastic pyrolysis is an
energy-efficient process. Based on the results and skilled gained from the design and
operation of the semi-scale plant, a commercial plant for pyrolysis of post-consumer
PE, PP, and PS could be designed. This technology can be applied to significantly
reduce the conventional landfill or incineration of waste plastics.

185
8.2. Future work
In order to commercialise the pyrolysis technology to recycling of the waste plastics
and to better understand the pyrolysis process, the following work is recommended
for further studies:
- In the semi-scale plant, the current continuous feeding system has minor leaks and
needs some modification. The feeding system should be able to control the
required feeding rate and prevent back-flow of the high temperature pyrolysis
vapour. On the other hand, the oxygen leaking into the feeder must be prevented.
Better and effective distillation columns should be applied on the semi-scale plant
for refining of the pyrolysis products.

- The effect of contamination in post-consumer plastics is still not clear due to the
variation of the contamination on different post-consumer plastics. Virgin and
post-consumer plastics on the process and the distribution of the product should
be investigated on the semi-scale plant. The detailed interaction among different
plastic materials during the cracking reactions is unknown, thus further
investigation is needed to quantitatively analyse the interaction effect of different
post-consumer plastics. This could be very valuable for commercialization of the
technology.

- The non-condensable gases were flared off in the experiment. It would be
valuable to collect some of the gases and investigate its composition. The diesel
range product should be separated out of the condensed products in the semi-scale
plant. The diesel range product should be tested in accordance to New Zealand
diesel requirements standard for the properties of commercial uses. It is
worthwhile to add hydrogen into the reaction to saturate the hydrocarbons thus to
modify the product to increase the target diesel products. Hydrogenation can
significantly improve the product quality towards transport use. Many oil refinery
186
factories apply this process to convert alkenes into alkane in order to get higher
stability oil.

187
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